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Inorganics
Number of Followers: 1  Open Access journalISSN (Online) 2304-6740 Published by MDPI  [258 journals]
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- Inorganics, Vol. 11, Pages 347: Synthesis of Ti-Ni and Zr-Ni
Core–Shell Particles Using Galvanic Replacement
Authors: Alexander F. Dresvyannikov, Leonid E. Kalugin, Ekaterina V. Petrova
First page: 347
Abstract: This article focuses on the galvanic replacement synthesis of Ti-Ni and Zr-Ni metal systems with a “core-shell” structure, which are potential precursors for intermetallics. The authors defined effective synthesis parameters and formation features of polymetallic systems characterized by granulometric, phase, and elemental composition. X-ray fluorescence and X-ray phase analysis methods showed that the deposition of nickel on dispersed titanium and zirconium leads to the production of test samples with phase composition representing a mechanical mixture of Ni and Ti, and Ni and Zr. The method of X-ray fluorescence analysis showed that the presence of hydrofluoric acid with a 0.5-1.5 M concentration results in the formation of fixed quantitative ratios of elements in the precipitate, which allows the quantitative composition of dispersed systems “titanium-nickel” and “zirconium-nickel” to be regulated within a relatively wide range. Scanning electron microscopy proved that all synthesized systems are characterized by a highly porous structure that follows the titanium and zirconium particle surface contour and the presence of spherical nanoscale subunits on the formed particle surface.
Citation: Inorganics
PubDate: 2023-08-24
DOI: 10.3390/inorganics11090347
Issue No: Vol. 11, No. 9 (2023)
- Inorganics, Vol. 11, Pages 348: Anion Capture at the Open Core of a
Geometrically Flexible Dicopper(II,II) Macrocycle Complex
Authors: Sam H. Brooks, Corey A. Richards, Patrick J. Carroll, Michael R. Gau, Neil C. Tomson
First page: 348
Abstract: Multicopper active sites for small molecule activation in materials and enzymatic systems rely on controlled but adaptable coordination spheres about copper clusters for enabling challenging chemical transformations. To translate this constrained flexibility into molecular multicopper complexes, developments are needed in both ligand design for clusters and synthetic strategies for modifying the cluster cores. The present study investigates the chemistry of a class of pyridyldiimine-derived macrocycles with geometrically flexible aliphatic linkers of varying lengths (nPDI2, n = 2, 3). A series of dicopper complexes bound by the nPDI2 ligands are described and found to exhibit improved solubility over their parent analogs due to the incorporation of 4-tBu groups on the pyridyl units and the use of triflate counterions. The ensuing synthetic study investigated methods for introducing various bridging ligands (µ-X; X = F, Cl, Br, N3, NO2, OSiMe3, OH, OTf) between the two copper centers within the macrocycle-supported complexes. Traditional anion metathesis routes were unsuccessful, but the abstraction of bridging halides resulted in “open-core” complexes suitable for capturing various anions. The geometric flexibility of the nPDI2 macrocycles was reflected in the various solid-state geometries, Cu–Cu distances, and relative Cu coordination spheres on variation in the identity of the captured anion.
Citation: Inorganics
PubDate: 2023-08-24
DOI: 10.3390/inorganics11090348
Issue No: Vol. 11, No. 9 (2023)
- Inorganics, Vol. 11, Pages 349: Reactivity of Open-Shell Metallofullerene
Anions: Synthesis, Crystal Structures, and Electrochemical Properties of
Benzylated Gd@C2v-C82
Authors: Xinyi Zhou, Yang-Rong Yao, Yajing Hu, Le Yang, Shaoting Yang, Yilu Zhang, Qianyan Zhang, Ping Peng, Peng Jin, Fang-Fang Li
First page: 349
Abstract: The reactivity of the open-shell Gd@C2v-C82 with different charge states towards benzyl bromide was investigated. [Gd@C2v-C82]3− exhibited enhanced activity relative to Gd@C2v-C82 and [Gd@C2v-C82]−. The structural characterizations, including MALDI-TOF MS, UV-vis-NIR, and single crystal X-ray diffraction, indicate the formation of isomeric benzyl monoadducts of Gd@C2v-C82. All three monoadducts contain 1:1 mirror-symmetric enantiomers. Additionally, the addition of the benzyl group and its specific position result in distinct electrochemical behavior of the products compared to the parent Gd@C2v-C82. Theoretical studies demonstrate that only [Gd@C2v-C82]3− has a HOMO energy level that matches well with the LUMO energy level of the PhCH2 radical, providing a rationalization for the observed significantly different reactivity.
Citation: Inorganics
PubDate: 2023-08-25
DOI: 10.3390/inorganics11090349
Issue No: Vol. 11, No. 9 (2023)
- Inorganics, Vol. 11, Pages 350: Synthesis, X-ray Structure, and Hirshfeld
Analysis of [Ag(3-amino-5,6-dimethyl-1,2,4-triazine)(NO3)]n: A Potent
Anticancer and Antimicrobial Agent
Authors: Mostafa A. El-Naggar, Morsy A. M. Abu-Youssef, Matti Haukka, Assem Barakat, Mona M. Sharaf, Saied M. Soliman
First page: 350
Abstract: The [Ag(3ADMT)(NO3)]n complex was synthesized by the self-assembly of 3-amino-5,6-dimethyl-1,2,4-triazine (3ADMT) and AgNO3. Its molecular structure was analyzed utilizing FTIR spectra, elemental analysis, and single crystal X-ray diffraction (SC-XRD). There is one crystallographically independent Ag atom, which is tetra-coordinated by two nitrogen atoms from two 3ADMT and two oxygen atoms from two nitrate anions where all ligand groups are acting as connectors between the Ag1 sites. The geometry around the Ag(I) center is a distorted tetrahedron with a AgN2O2 coordination sphere augmented by strong argentophilic interactions between Ag atoms, which assist the aggregation of the complex units in a wavy-like and coplanar pattern to form a one-dimensional polymeric chain. The O...H (37.2%) and N...H (18.8%) intermolecular interactions contributed significantly to the molecular packing based on Hirshfeld surface analysis. The [Ag(3ADMT)(NO3)]n complex demonstrates promising cytotoxicity against lung (IC50 = 2.96 ± 0.31 μg/mL) and breast (IC50 = 1.97 ± 0.18 μg/mL) carcinoma. This remarkable cytotoxicity exceeds those of 3ADMT, AgNO3, and the anticancer medication cis-platin towards the tested cancer cell lines. In addition, the complex has a wide-spectrum antimicrobial action where the high antibacterial potency of the [Ag(3ADMT)(NO3)]n complex against P. vulgaris (MIC = 6.1 µg/mL) and B. subtilis (MIC = 17.2 µg/mL) could be comparable to the commonly used drug Gentamycin (MIC = 4.8 µg/mL). These results confirm that the components of the [Ag(3ADMT)(NO3)]n complex work together synergistically, forming a powerful multifunctional agent that could be exploited as an effective antimicrobial and anticancer agent.
Citation: Inorganics
PubDate: 2023-08-25
DOI: 10.3390/inorganics11090350
Issue No: Vol. 11, No. 9 (2023)
- Inorganics, Vol. 11, Pages 351: The Synthesis and Crystal Structure of Six
Quaternary Lithium-Alkaline Earth Metal Alumo-Silicides and
Alumo-Germanides, A2LiAlTt2 (A = Mg, Ca, Sr, Ba; Tt = Si, Ge)
Authors: Paraskevi Kontomaris, Gregory M. Darone, Laura C. Paredes-Quevedo, Svilen Bobev
First page: 351
Abstract: Reported are the synthesis and structural characterization of a series of quaternary lithium-alkaline earth metal alumo-silicides and alumo-germanides with the base formula A2LiAlTt2 (A = Ca, Sr, Ba; Tt = Si, Ge). To synthesize each compound, a mixture of the elements with the desired stoichiometric ratio was loaded into a niobium tube, arc welded shut, enclosed in a silica tube under vacuum, and heated in a tube furnace. Each sample was analyzed by powder and single-crystal X-ray diffraction, and the crystal structure of each compound was confirmed and refined from single-crystal X-ray diffraction data. The structures, despite the identical chemical formulae, are different, largely dependent on the nature of the alkaline earth metal. The differing cation determines the structure type—the calcium compounds are part of the TiNiSi family with the Pnma space group, the strontium compounds are isostructural with Na2LiAlP2 with the Cmce space group, and the barium compounds crystallize with the PbFCl structure type in the P4/nmm space group. The anion (silicon or germanium) only impacts the size of the unit cell, with the silicides having smaller unit cell volumes than the germanides.
Citation: Inorganics
PubDate: 2023-08-26
DOI: 10.3390/inorganics11090351
Issue No: Vol. 11, No. 9 (2023)
- Inorganics, Vol. 11, Pages 352: Synthesis of Copper/Sulfur Co-Doped
TiO2-Carbon Nanofibers as Catalysts for H2 Production via NaBH4 Hydrolysis
Authors: Ahmed Abutaleb
First page: 352
Abstract: Copper/sulfur co-doped titanium dioxide-carbon nanofibers (Cu,S-codoped TiO2 NPs, decorated-CNFs) catalysts were synthesized using the electrospinning process to produce composite nanofibers (NFs). These composite NFs were utilized for the hydrolysis of sodium borohydride (SBH) to generate hydrogen gas (H2), taking advantage of their catalytic properties. The experimental results demonstrated that using 100 mg of composite NFs yielded the highest catalytic activity for H2 production, generating 79 mL of H2 gas within 6 min at 25 °C and 1000 revolutions per minute (rpm) using 1 mmol of SBH. As the catalyst dosage was reduced from 100 mg to 75, 50, and 25 mg, the reaction time increased by 9, 13, and 18 min, respectively. Kinetic studies revealed that the reaction rate followed a first-order reaction, indicating a direct proportionality between the rate of reaction and the catalyst amount. Additionally, it was observed that the concentration of SBH had no influence on the reaction rate, suggesting a zero-order reaction. Increasing the reaction temperature resulted in a reduced reaction time. The activation energy was determined to be 26.16 kJ mol−1. The composite NFs maintained their superior performance over five iterations. These findings suggest that composite nanofibers have the potential to serve as a cost-effective alternative to expensive catalysts in hydrogen production.
Citation: Inorganics
PubDate: 2023-08-27
DOI: 10.3390/inorganics11090352
Issue No: Vol. 11, No. 9 (2023)
- Inorganics, Vol. 11, Pages 353: Crystal Structures of DNA Intercalating
Agents Dipyrido[3,2-f:2′,3′-h]quinoxaline (dpq),
(Benzo[i]dipyrido[3,2-a:2′,3′c]phenazine (dppn), and
[Ir(ppy)2(dppn)][PF6] (Where Hppy = 2-Phenylpyridine)
Authors: Marisa James, Madelyn R. Shevlin, Thomas B. Green, Megan M. Smart, Colin D. McMillen, Jared A. Pienkos
First page: 353
Abstract: Pyrazino-phenanthroline ligands are commonly used with transition metals as DNA intercalation agents. Herein, we report the characterization of two commonly utilized pyrazino-phenanthroline ligands, dipyrido[3,2-f:2′,3′-h]quinoxaline (dpq) and (benzo[i]dipyrido[3,2-a:2′,3′c]phenazine (dppn), by single-crystal X-ray diffraction. Additionally, the characterization of [Ir(ppy)2(dppn)][PF6], where Hppy = 2-phenylpyridine, by single-crystal X-ray diffraction is described. Both the dpq and dppn ligands crystallize as chloroform solvates where the chloroform molecule occupies the equivalent binding pocket of a metal in metal complexes of these ligands. These pyrazino-phenanthrolines are largely planar, with the dppn ligand displaying a slight twist. When the dppn ligand is coordinated to iridium(III), the dppn ligand on the resulting complex displays a significant degree of bending along the longitudinal direction of the ligand. This iridium (III) complex crystallizes as a CH2Cl2 and Et2O solvate and due to the volatility of these solvents these crystals are only stable for a few seconds outside of the mother liquor. The structures of the free ligands and the [Ir(ppy)2(dppn)][PF6] complex all display extensive π stacking interactions.
Citation: Inorganics
PubDate: 2023-08-29
DOI: 10.3390/inorganics11090353
Issue No: Vol. 11, No. 9 (2023)
- Inorganics, Vol. 11, Pages 354: Enhancing the Tribo-Mechanical Performance
of LDPE Nanocomposites Utilizing Low Loading Fraction Al2O3/SiC Hybrid
Nanostructured Oxide Fillers
Authors: Ibrahim A. Alnaser, Ahmed Fouly, Muhammad Omer Aijaz, Jabair A. Mohammed, Mahmoud B. Elsheniti, Sameh A. Ragab, Hany S. Abdo
First page: 354
Abstract: This research work highlights the tribomechanical investigations of using a low loading fraction of two ceramics combinations, Alumina (Al2O3) and Silicon Carbide (SiC) as reinforcement for Low-density Polyethylene (LDPE) matrix. The hybrid additives with different weight percentages (0.1 + 0.1, 0.25 + 0.25 and 0.5 + 0.5 wt%) were mixed with LDPE matrix and the degree of homogeneity was controlled using double-screw extruder prior to fabricating the composite samples via the injection molding machine. The nanoparticles fillers were characterized by field emission scanning electron microscope (FESEM), EDX and particle size analyzer to check its morphology, composition and size distribution. Thermogravimetric analyzer (TGA) and melting flow index (MFI) were performed for the fabricated nanocomposites samples. The mechanical properties of the nanocomposite were evaluated by performing tensile test, bending test and Shore-D hardness test, while the tribological performance was investigated using a ball on desk apparatus under different applied loads and sliding times. Moreover, in order to confirm the load-carrying capability of the composite, contact stresses was measured via finite element model using ANSYS software. The results show that the incorporation of low fraction hybrid ceramic nanoparticles can contributed positively in the tribological and mechanical properties. Based on the experimental results, the maximum improvement in the tensile strength was 5.38%, and 8.15% for hardness LDPE with 0.5 Al2O3 and 0.5 SiC, while the lowest coefficient of friction was noticed under normal load of 10 N, which was approximately 12.5% for the same composition. The novel approach of incorporating low fraction hybrid ceramic nanoparticles as reinforcement for LDPE matrix is investigated, highlighting their positive contributions to the tribological and mechanical properties of the resulting nanocomposites.
Citation: Inorganics
PubDate: 2023-08-29
DOI: 10.3390/inorganics11090354
Issue No: Vol. 11, No. 9 (2023)
- Inorganics, Vol. 11, Pages 355: Synthesis of Nanostructured Alumina from
Byproduct Aluminum Filings: Production and Characterization
Authors: Muayad Esaifan, Ahmed Al-Mobydeen, Ahmed N. Al-Masri, Abdelmnim M. Altwaiq, Bety S. Al-Saqarat, Wadah Mahmoud, Arwa Hamaideh, Iessa Sabbe Moosa, Imad Hamadneh, Ehab AlShamaileh
First page: 355
Abstract: Aluminum oxide production from aluminum filings, which are a byproduct of several industrial machining processes and cannot be recycled to attain bulk aluminum (Al), is vital due to its wide use in scientific research and industry. The goal of this paper is to produce ultrafine and down-to-the-nanoscale alumina powder (Al2O3), starting from a waste Al filings. The microstructure and composition of the starting Al used were investigated using scanning electron microscopy (SEM), which was equipped with an attached energy dispersive spectrometer (EDS) unit. The results of this investigation confirmed that the starting Al was mainly Al–Mg alloy. Al2O3 was produced using two routes: The first involved the burning of aluminum hydroxide Al(OH)3 that was precipitated from aluminum chloride solution (AlCl3) resulting from dissolving the Al filings in 2M HCl. The second route involved direct precipitation as a reaction product of aluminum chloride with sodium carbonate solution. The Al2O3 produced using both routes, as well as the intermediate product Al(OH)3, were studied by SEM. The results demonstrate that the nanoscale range size was reached after milling of the produced Al2O3. Following thorough washing with distilled water, the EDS and the XRD techniques confirmed the formation of Al2O3, with no residual salt detected. The EDS results showed that the ratios of Al and O in the produced Al2O3 were about 96% of the ideal compound ratios. The XRD analysis also revealed the amorphous structure of the standard and the produced Al(OH)3, whereas the phases of the produced Al2O3 were either crystalline or amorphous. In our study, the Al2O3 percentage yield was about 77%, and this value obviously depends on the percentage of Al dross in the original Al filings. Overall, this research provides a novel contribution to the production of alumina powder in the nano-range starting from an aluminum filings byproduct, thereby reducing the dependence on known sources of aluminum.
Citation: Inorganics
PubDate: 2023-08-29
DOI: 10.3390/inorganics11090355
Issue No: Vol. 11, No. 9 (2023)
- Inorganics, Vol. 11, Pages 356: The “Periodic Table” of
1-methylbenzotriazole: Zinc(II) Complexes
Authors: Christina Stamou, Eleftheria Barouni, John C. Plakatouras, Michael M. Sigalas, Catherine P. Raptopoulou, Vassilis Psycharis, Evangelos G. Bakalbassis, Spyros P. Perlepes
First page: 356
Abstract: In an attempt to fill in the empty Zn position in the “Periodic Table” of 1-methylbenzotriazole (Mebta), reactions between Zn(II) sources and this ligand were carried out. The detailed synthetic studies provided access to complexes [ZnX2(Mebta)2] (X = Cl, 1; X = Br, 3; X = I, 4), (MebtaH)2[ZnCl4] (2), tet-[Zn(NO3)2(Mebta)2] (5), oct-[Zn(NO3)2(Mebta)2] (6), and [Zn(Mebta)4](Y)2 [Y = ClO4, 7; Y = PF6, 8]. Solid-state thermal decomposition of 2 leads to 1 in quantitative yield. The structures of 3, 4, 5, 6, and 7 were determined by single-crystal crystallography. The structures of the remaining complexes were proposed based on spectroscopic evidence. In all compounds, Mebta behaves as monodentate ligand using the nitrogen of the position 3 as donor. Complexes 1–4, 7, and 8 are tetrahedral. Complexes 5 and 6 are isostoichiometric and their preparation in pure forms depends on the reaction conditions; in the former the ZnII atom has a tetrahedral geometry, whereas in the latter the metal ion is octahedral. This case of rare isomerism arises from the monodentate (in 5) vs. bidentate (in 6) coordination of the nitrato groups. Extensive π–π stacking interactions and non-classical H bonds build interesting 3D architectures in the structurally characterized complexes. The compounds were characterized by IR, far-IR, and Raman spectroscopies in the solid state, and the data were interpreted in terms of the structures (known or proposed) of the complexes and the coordination modes of the organic and inorganic ligands involved. The solid-state structures of the complexes are not retained in solution, as proven by NMR (1H, 13C[1H]) spectroscopy and molar conductivity data. The thermal decomposition study of 1 and 3 leads to stable intermediates with 1:1 stoichiometry, i.e., ZnX2(Mebta). Based on far-IR spectra, polymeric tetrahedral structures are possible with simultaneous presence of terminal and bridging X− groups. Liquid-phase ab initio (MP2) and gas-phase DFT calculations, performed on Mebta and the nitrato complexes, respectively, shed light on the tendency of Mebta for N3-coordination, and the existence and relative stabilities of 5 and 6.
Citation: Inorganics
PubDate: 2023-08-29
DOI: 10.3390/inorganics11090356
Issue No: Vol. 11, No. 9 (2023)
- Inorganics, Vol. 11, Pages 357: Synthesis, X-ray Structure, Hirshfeld
Surface Analysis and Antimicrobial Assessment of Tetranuclear s-Triazine
Hydrazine Schiff Base Ligand
Authors: Hessa H. Al-Rasheed, Sarah A. AL-khamis, Ayman El-Faham, Assem Barakat, Alexandra M. Z. Slawin, John Derek Woollins, Saied M. Soliman
First page: 357
Abstract: The unexpected tetranuclear [Cu4(DPPT)2Cl6] complex was obtained by self-assembly of CuCl2.2H2O and (E)-2,4-di(piperidin-1-yl)-6-(2-(1-(pyridin-2-yl)ethylidene)hydrazinyl)-1,3,5-triazine, (HDPPT) in ethanol. In this tetranuclear [Cu4(DPPT)2Cl6] complex, the organic ligand acts as mononegative chelate bridging two crystallographically independent Cu(II) sites. The DPPT− anion acts as a bidentate ligand with respect to Cu(1), while it is a tridentate for Cu(2). The Cu(1)N2Cl3 and Cu(2)N3Cl spheres have square pyramidal and square planar coordination geometries with some distortion, respectively. Two of the chloride ions coordinating the Cu(1) are bridging between two crystallographically related Cu(1) sites connecting two [Cu2(DPPT)Cl3] units together, leading to the tetranuclear formula [Cu4(DPPT)2Cl6]. The packing of the [Cu4(DPPT)2Cl6] complex is dominated by C-H…Cl contacts, leading to one-dimensional hydrogen-bond polymeric structure. According to Hirshfeld surface analysis of molecular packing, the non-covalent interactions H…H, Cl…H, Cl…C, C…H, and N…H are the most significant. Their percentages are 52.8, 19.0, 3.2, 7.7, and 9.7%, respectively. Antimicrobial assessment showed good antifungal activity of the Cu(II) complex against A. fumigatus and C. albicans compared to Ketoconazole as positive control. Moreover, the [Cu4(DPPT)2Cl6] complex has higher activity against Gram-positive bacteria than Gentamycin as positive control. The opposite was observed when testing the tetranuclear [Cu4(DPPT)2Cl6] complex against the Gram-negative bacteria.
Citation: Inorganics
PubDate: 2023-08-30
DOI: 10.3390/inorganics11090357
Issue No: Vol. 11, No. 9 (2023)
- Inorganics, Vol. 11, Pages 358: Boron Applications in Prevention,
Diagnosis and Therapy for High Global Burden Diseases
Authors: Marvin A. Soriano-Ursúa
First page: 358
Abstract: The role of boron-containing compounds (BCCs) in medicine is growing [...]
Citation: Inorganics
PubDate: 2023-08-30
DOI: 10.3390/inorganics11090358
Issue No: Vol. 11, No. 9 (2023)
- Inorganics, Vol. 11, Pages 359: The Critical Role of Ligand Flexibility on
the Activity of Free and Immobilized Mn Superoxide Dismutase Mimics
Authors: Micaela Richezzi, Sharon Signorella, Claudia Palopoli, Nora Pellegri, Christelle Hureau, Sandra R. Signorella
First page: 359
Abstract: In low-molecular-weight Mn superoxide dismutase (SOD) mimics, the ligand plays a key role in tuning the reactivity of the metal center with O2•−. We used three ligands differing in their donor sites, flexibility and/or charge, to compare the redox properties and SOD activity of the resulting Mn complexes: 1,3-bis[(pyridin-2-ylmethyl)(propargyl)amino]propane (pypapn), 1,3-bis(pyridin-2-ylmethyleneamino)propane (py2pn) and 1,4-bis(salicylidenamino)butane (H2salbn). These ligands afford Mn complexes that, in aqueous solution, exist as mononuclear species [Mn(II)(pypapn)(H2O)2]2+, [Mn(II)(py2pn)(H2O)2]2+ and [Mn(III)(salbn)(H2O)2]+. The relative reactivity of these compounds with O2•− at pH 7.8, [Mn(pypapn)(H2O)2]2+ > [Mn(salbn)(H2O)2]+ > [Mn(py2pn)(H2O)2]2+, is independent of the redox potential but strongly depends on the ligand flexibility which becomes a critical feature when the reaction occurs through an inner-sphere electron-transfer mechanism. Immobilization was used to isolate and protect the catalyst from dissociation or dimerization during catalysis. [Mn(pypapn)(H2O)2]2+, with the alkyne group, was covalently grafted to azide functionalized mesoporous silica through click chemistry, while [Mn(py2pn)(solv)2]2+ and [Mn(salbn)(solv)2]+ were encapsulated in SBA-15 mesoporous silica through ionic exchange. The retention or enhancement of the SOD activity and the improved stability of the covalently attached catalyst and the doubly charged complex encapsulated in the silica pores, make them suitable for use in aqueous media.
Citation: Inorganics
PubDate: 2023-08-30
DOI: 10.3390/inorganics11090359
Issue No: Vol. 11, No. 9 (2023)
- Inorganics, Vol. 11, Pages 360: Ce0.8Y0.2O2-δ-BaCe0.8Y0.2O3-δ
Dual-Phase Hollow Fiber Membranes for Hydrogen Separation
Authors: Yuepeng Hei, Zuojun Lu, Claudia Li, Jian Song, Bo Meng, Naitao Yang, Sibudjing Kawi, Jaka Sunarso, Xiaoyao Tan, Shaomin Liu
First page: 360
Abstract: Partial oxidation of methane (POM) is a prominent pathway for syngas production, wherein the hydrogen in syngas product can be recovered directly from the reaction system using a hydrogen (H2)-permeable membrane. Enhancing the efficiency of this H2 separation process is a current major challenge. In this study, Ce0.8Y0.2O2-δ-BaCe0.8Y0.2O3-δ (YDC-BCY) hollow fiber (HF) membranes were developed and characterized for their H2 permeation fluxes. Firstly, YDC and BCY ceramic powders were synthesized using the sol-gel method, followed by the fabrication of YDC-BCY dual-phase ceramic HF membranes using a combined phase inversion–sintering process. Characterization using SEM, powder XRD, EDS, and electrical conductivity tests confirmed the phases of the prepared powders and HF membranes. Well-structured YDC and BCY powders with uniform particle sizes were obtained after calcination at 900 °C. With the addition of 1 wt.% Co2O3 as a sintering aid, the YDC-BCY dual-phase HF membrane achieved densification after sintering at 1500 °C. Subsequently, the influences of sweep gas composition and temperature on the hydrogen permeation of the YDC-BCY HF membranes with YDC/BCY molar ratios of 2:1, 3:1, and 4:1 were investigated. At 1000 °C and a sweep-gas flow rate of 120 mL·min−1, the YDC-BCY HF membrane with a YDC/BCY molar ratio of 4:1 exhibited a peak hydrogen flux of 0.30 mL·min−1 cm−2. There is significant potential for improving the hydrogen permeation of dual-phase ceramic membranes, with future efforts aimed at reducing dense layer thickness and enhancing the membrane material’s electronic and proton conductivities.
Citation: Inorganics
PubDate: 2023-09-01
DOI: 10.3390/inorganics11090360
Issue No: Vol. 11, No. 9 (2023)
- Inorganics, Vol. 11, Pages 361: Phase Behavior and Defect Structure of
HoBaCo2O6-δ
Authors: Roman E. Yagovitin, Dmitry S. Tsvetkov, Ivan L. Ivanov, Dmitry A. Malyshkin, Vladimir V. Sereda, Andrey Yu. Zuev
First page: 361
Abstract: The differential scanning calorimetry study showed that the double perovskite HoBaCo2O6-δ (HBC), depending on its oxygen content, undergoes three phase transitions in the temperature range 298–773 K. Their origin was tentatively explained using the relevant literature data. For the single-phase tetragonal HBC, the oxygen nonstoichiometry dependences on the oxygen partial pressure were investigated by thermogravimetric and flow reactor methods in the intermediate-temperature range of 573–773 K. The proposed defect structure of HBC was successfully verified using the obtained data on its oxygen nonstoichiometry combined with those reported earlier. As a result, the values of the thermodynamic parameters (∆Hi∘, ∆Si∘) of the defect reactions proceeding in HBC were determined. The defect structure of HBC was shown to be similar to that of YBaCo2O6-δ (YBC) likely due to similar ionic radii of Ho3+ and Y3+.
Citation: Inorganics
PubDate: 2023-09-05
DOI: 10.3390/inorganics11090361
Issue No: Vol. 11, No. 9 (2023)
- Inorganics, Vol. 11, Pages 362: Luminescent Cadmium(II)-Based 12-MC-4
Metallacrown Complex with 2-Methylmercaptobenzohydroxamic Acid Ligand
Authors: Sriram Sundaresan, Christoph Gamer, Mortiz J. Förster, Luca M. Carrella, Eva Rentschler
First page: 362
Abstract: We reported herein the synthesis, structure determination and emission properties of a cubic molecular Cd(II) coordination cluster whose faces are composed of 12-MC-4 metallacrown units built up from Cd2+ and 2-methylmercaptobenzohydroxamic acid (LmmbHA), resulting in [CdII14(LmmbHA)12(µ6−O)(DMF)10](ClO4)2·3H2O. The polynuclear complex obtained was characterised by single crystal X-ray diffraction at 193 K. The bulk sample was also analysed by elemental analysis. UV-Vis and emission spectra of the complex were measured in chloroform, as well as the emission spectra of the ligand for comparison. The results of the emission studies revealed that both the ligand and the complex are weakly emissive.
Citation: Inorganics
PubDate: 2023-09-05
DOI: 10.3390/inorganics11090362
Issue No: Vol. 11, No. 9 (2023)
- Inorganics, Vol. 11, Pages 363: Efficient Disposal of Basic Fuchsin Dye
from Aqueous Media Using ZrO2/MgMn2O4/Mg(Mg0.333Mn1.333)O4 as a Novel and
Facilely Synthesized Nanocomposite
Authors: Asma S. Al-Wasidi, Mohamed Khairy, Babiker Y. Abdulkhair, Ehab A. Abdelrahman
First page: 363
Abstract: In this work, amorphous and crystalline novel products based on Zr, Mg, and Mn were facilely fabricated through the Pechini sol–gel procedure using inexpensive chemicals and an uncomplicated apparatus. Also, these products showed high efficiency as novel adsorbents in getting rid of basic fuchsin dye from aqueous solutions. The adsorbent, which was fabricated before calcination, was abbreviated as KE. In addition, the adsorbents, which were created at 500 and 700 °C, were designated as KE500 and KE700, respectively. The created adsorbents were characterized using high-level transmission electron microscopy (HR-TEM), X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS), N2 adsorption/desorption analyzer, and field emission scanning electron microscope (FE-SEM). The XRD showed that the KE adsorbent is amorphous, whereas the KE500 and KE700 adsorbents are mixtures of ZrO2, MgMn2O4, and Mg(Mg0.333Mn1.333)O4 nanostructures. The HR-TEM exhibited that the KE adsorbent consists of very fine irregular shapes, whereas the KE500 adsorbent contains quasi-spherical particles with a mean diameter of 45.16 nm. Furthermore, the HR-TEM exhibited that the KE700 adsorbent consists of polyhedral shapes with a mean diameter of 76.28 nm. Furthermore, the BET surface area of the KE, KE500, and KE700 adsorbents is 67.85, 20.15, and 13.60 m2/g, respectively. Additionally, the elimination of basic fuchsin dye by the KE, KE500, and KE700 adsorbents is exothermic, physical in nature, and follows the pseudo-first-order as well as Langmuir equations. Further, the maximum uptake capabilities of the KE, KE500, and KE700 adsorbents toward basic fuchsin dye are 239.81, 174.83, and 93.19 mg/g, respectively.
Citation: Inorganics
PubDate: 2023-09-07
DOI: 10.3390/inorganics11090363
Issue No: Vol. 11, No. 9 (2023)
- Inorganics, Vol. 11, Pages 364: Isocyanide Cycloaddition and Coordination
Processes at Trigonal Phosphinidene-Bridged MoRe and MoMn Complexes
Authors: M. Angeles Alvarez, M. Esther García, Daniel García-Vivó, Miguel A. Ruiz, Patricia Vega
First page: 364
Abstract: Heterometallic phosphinidene complexes are appealing species for the construction of novel organophosphorus ligands thanks to the high reactivity expected from the combination of M-P multiple bonding and the intrinsically different electronic and coordination preferences of the distinct metals. In a preliminary study, we found that the heterobimetallic complex [MoReCp(μ-PMes*)(CO)6] (Mes* = 2,4,6-C6H2tBu3) reacted with CN(p-C6H4OMe) via [2+1]-cycloaddition to form a novel azaphosphallene complex. We have now examined in detail the reactions of the above complex and those of its MoMn analogue with different isocyanides, which turned out to be strongly dependent on experimental conditions and on the size of the substituent at the isocyanide. All the products formed follow from one or several of the following reaction pathways: (i) CO substitution by CNR; (ii) addition of CNR at the group 7 metal centre; and (iii) [2+1] cycloaddition of isocyanide at a Mo=P bond to form azaphosphallene groups, with the former process being dominant in reactions at room temperature and for the Mn system. In contrast, low-temperature reactions of the Re system favoured the addition processes, with the [2+1] cycloaddition at Mo=P bonds only taking place at substrates without metal-metal bonds and when the size of the CNR group does not cause unbearable steric clashes when placed in between the Cp and Mes* groups.
Citation: Inorganics
PubDate: 2023-09-07
DOI: 10.3390/inorganics11090364
Issue No: Vol. 11, No. 9 (2023)
- Inorganics, Vol. 11, Pages 365: Dibromo- and Dichlorotriphenylphosphino
N-Acyclic Carbene Complexes of Platinum(II)—Synthesis and
Cytotoxicity
Authors: Anna Farasat, Luca Labella, Maria Luisa Di Paolo, Lisa Dalla Via, Simona Samaritani
First page: 365
Abstract: Some new dichloro- and dibromotriphenylphosphino isonitrile and N-acyclic (NAC) carbene complexes of platinum(II) were synthesized, starting from suitable dinuclear precursors. The reaction of cyclohexylisonitrile with trans-[Pt(μ-X)X(PPh3)]2, followed by the addition of N,N-diethylamine afforded the corresponding N-acyclic carbene (NAC)derivatives cis-[PtX2(PPh3)(NAC)] in 61–64% isolated yield. The cis geometry was attributed based on the comparison with known structures. The stability of the complexes in pure DMSO, DMSO/H2O, and DMSO/NaClaq mixtures was evaluated. While pure DMSO, as well as DMSO/H2O, did not affect the nature of either dichloro- or dibromo-compounds, dibromo derivatives were not stable in the presence of chloride ions. Since a high concentration of chloride ions is essential to perform in vitro cell assays, only dichlorocomplexes were tested as cytotoxic agents against HepG2 and human tumor cells. Among the tested complexes, NAC derivatives showed a moderate effect on MSTO-211H.
Citation: Inorganics
PubDate: 2023-09-08
DOI: 10.3390/inorganics11090365
Issue No: Vol. 11, No. 9 (2023)
- Inorganics, Vol. 11, Pages 366: Room-Temperature Hydrogen-Sensitive
Pt-SnO2 Composite Nanoceramics: Contrasting Roles of Pt Nano-Catalysts
Loaded via Two Different Methods
Authors: Jieting Zhao, Jiannan Song, Xilai Lu, Menghan Wu, Zhiqiao Yan, Feng Chen, Wanping Chen
First page: 366
Abstract: Soluble noble metal salts are widely used for loading noble metals as nano-catalysts in many applications. In this paper, Pt-SnO2 composite nanoceramics were prepared from SnO2 nanoparticles and H2PtCl6 using two Pt loading methods separately: for the solution reduction method, a H2PtCl6 solution was added to a suspension of SnO2 and zinc powder to form Pt on SnO2 nanoparticles, and for the impregnation method, Pt was formed from H2PtCl6 in the course of sintering. Although a series of samples prepared using both Pt loading methods showed a solid response to H2 at room temperature, the ones prepared using the solution reduction method exhibited much better room-temperature hydrogen-sensing characteristics. For two samples of 0.5 wt% Pt and sintered at 825 °C, the response value for the sample prepared using the solution reduction method was 9700 to 1% H2–20% O2-N2, which was much larger than the value of 145 for the sample prepared using the impregnation method. Samples prepared using the two Pt loading methods have similar microstructures characterized via XRD, FESEM, EDS, TEM, and HRTEM. However, the residual chlorine content in those using the impregnation method was higher than those using the solution reduction method according to the analysis. It is proposed that the striking difference in room-temperature hydrogen sensing characteristics among samples prepared using these two different Pt loading methods separately resulted from their different chlorine removal processes. This study demonstrates the importance of a proper method for loading noble metals from their soluble salts as nano-catalysts in many applications.
Citation: Inorganics
PubDate: 2023-09-09
DOI: 10.3390/inorganics11090366
Issue No: Vol. 11, No. 9 (2023)
- Inorganics, Vol. 11, Pages 367: Copper(I)/Triphenylphosphine Complexes
Containing Naphthoquinone Ligands as Potential Anticancer Agents
Authors: Celisnolia M. Leite, João H. Araujo-Neto, Adriana P. M. Guedes, Analu R. Costa, Felipe C. Demidoff, Chaquip D. Netto, Eduardo E. Castellano, Otaciro R. Nascimento, Alzir A. Batista
First page: 367
Abstract: Four new Cu/PPh3/naphtoquinone complexes were synthesized, characterized (IR, UV/visible, 1D/2D NMR, mass spectrometry, elemental analysis, and X-ray diffraction), and evaluated as anticancer agents. We also investigated the reactive oxygen species (ROS) generation capacity of complex 4, considering the well-established photochemical property of naphthoquinones. Therefore, employing the electron paramagnetic resonance (EPR) “spin trap”, 5,5-dimethyl-1-pyrroline N-oxide (DMPO) technique, we identified the formation of the characteristic •OOH species (hydroperoxyl radical) adduct even before irradiating the solution containing complex 4. As the irradiation progressed, this radical species gradually diminished, primarily giving rise to a novel species known as •DMPO-OH (DMPO + •OH radical). These findings strongly suggest that Cu(I)/PPh3/naphthoquinone complexes can generate ROS, even in the absence of irradiation, potentially intensifying their cytotoxic effect on tumor cells. Interpretation of the in vitro cytotoxicity data of the Cu(I) complexes considered their stability in cell culture medium. All of the complexes were cytotoxic to the lung (A549) and breast tumor cell lines (MDA-MB-231 and MCF-7). However, the higher toxicity for the lung (MRC5) and breast (MCF-10A) non-tumoral cells resulted in a low selectivity index. The morphological analysis of MDA-MB-231 cells treated with the complexes showed that they could cause decreased cell density, loss of cell morphology, and loss of cell adhesion, mainly with concentrations higher than the inhibitory concentration of 50% of cell viability (IC50) values. Similarly, the clonogenic survivance of these cells was affected only with concentrations higher than the IC50 values. An antimigratory effect was observed for complexes 1 and 4, showing around 20–40% of inhibition of wound closure in the wound healing experiments.
Citation: Inorganics
PubDate: 2023-09-09
DOI: 10.3390/inorganics11090367
Issue No: Vol. 11, No. 9 (2023)
- Inorganics, Vol. 11, Pages 368: Effects of Coloration of Spinel CoAl2O4
Cobalt Blue Pigments: Composition, Structure, and Cation Distribution
Authors: Weiran Zhang, Ziyu Li, Guohua Wu, Wei Wu, Hailan Zeng, Haiyun Jiang, Weili Zhang, Ruomei Wu, Qiong Xue
First page: 368
Abstract: Cobalt blue ceramic pigments mainly consisting of CoAl2O4 are subject to the difficulty of color control. Here, a perspective is reported regarding research on the reasons for color change based on the control of the heat treatment and ratio of components. Macroscopically, the composition of pigment powders determines the color. Microscopically, the crystallite characters including size, cation distribution, and structure have an important effect on the color. The ingredient, structural, and color properties of the pigment powders are analyzed using thermo gravimetry–differential scanning calorimetry (TG–DSC), X-ray diffraction (XRD) measurement, Rietveld refinement, energy dispersive spectrometer (EDS), and colorimetry analysis. The color is proven to be associated with cation distribution, such as that of Co2+ and Co3+. It is indicated that high heating temperature, long heating time, and a large proportion of Al3+ can, respectively, induce the Co2+ and Al3+ in tetrahedral and octahedral sites.
Citation: Inorganics
PubDate: 2023-09-14
DOI: 10.3390/inorganics11090368
Issue No: Vol. 11, No. 9 (2023)
- Inorganics, Vol. 11, Pages 369: Synthesis of High-Crystallinity Mg-Al
Hydrotalcite with a Nanoflake Morphology and Its Adsorption Properties for
Cu2+ from an Aqueous Solution
Authors: Nai-Cai Xu, Dan-Dan Shi, Ying Zhang, Kai-Peng Zhong, Jing Liu, Qi Zhao, Qiang Gao, Shao-Ju Bian
First page: 369
Abstract: A magnesium–aluminum-layered double hydroxide (Mg-Al LDH) with a nano-lamellar morphology was prepared by using a homogeneous precipitation and hydrothermal method, and a calcination product (Mg-Al LDO) of the Mg-Al LDH was also obtained in this work. The XRD, TEM, SEM, FTIR, N2 ad/desorption, and TG-DTG techniques were employed to characterize the microstructures, morphologies, and thermostability levels of these two materials in detail. The results showed that both the Mg-Al LDH and Mg-Al LDO had mesoporous structures and nanoplate morphologies, with diameters of 50~200 nm. The Mg-Al LDH was transformed into Mg-Al LDO at 773 K in an air atmosphere. The adsorption properties of the Mg-Al LDH were investigated systematically with a copper chloride solution as a simulated waste. The experimental results demonstrated that the pH value of the solution had an obvious influence on its Cu2+ adsorption capacity, and the optimal pH value was approximately 5.0. The adsorption kinetics results showed that the Mg-Al LDH had a rapid adsorption rate, and the equilibrium adsorption capacity was 62.11 mg/g. Additionally, the Cu2+ adsorption could be commendably described using a pseudo-second-order model, demonstrating that the adsorption behavior is regulated by chemical sorption. The adsorption thermodynamic results indicated that the adsorption process was spontaneous at temperatures above 318 K. Moreover, the ΔG0 values decreased as the temperature was raised, which indicated that a higher temperature can cause a greater impetus for Cu2+adsorption. In addition, the positive values of the ΔH0 indicated that the Cu2+ adsorption was endothermic, and the positive ΔS0 values revealed an increase in the confusion at the solid–liquid interface of the adsorbent.
Citation: Inorganics
PubDate: 2023-09-15
DOI: 10.3390/inorganics11090369
Issue No: Vol. 11, No. 9 (2023)
- Inorganics, Vol. 11, Pages 370: Probe-Sonicated Synthesis of CuO–ZnO
Hybrid Nanocomposite for Photocatalytic and Supercapacitor Applications
Authors: Amal BaQais, Mir Waqas Alam, Mohd Farhan, Ghazala Muteeb, Nassiba Allag, Shehla Mushtaq
First page: 370
Abstract: An ultrasound-assisted probe sonication route effectively prepared pure CuO and two-dimensional CuO-ZnO nanocomposites (NCs) for different ratios of CuO and ZnO, and the experimental and theoretical methods investigated the structural, photocatalytic, and electrochemical properties. The XRD (X-ray diffraction) patterns revealed a crystallite size (D) range of 25 to 31 nm for pure CuO and CuO-ZnO NCs. According to calculations, the sample’s optical energy bandgap value (Eg) for the NCs is between 1.72 and 2.15 eV. Under UV light irradiation, the photocatalytic discoloration of pure CuO and CuO-ZnO NCs on fast blue (FB) dye was assessed. Under the influence of UV light, the CuO with 10% ZnO composite degrades 83.4% of the dye, which is greater than pure CuO and other NCs. The electrochemical properties of the prepared NCs materials have been studied using cyclic voltammetry and electrochemical impedance spectroscopy (EIS). The specific capacitance values were found to be 248 Fg−1, 301 Fg−1, 352 Fg−1, and 277 Fg−1 for CuO, CuO + 5% ZnO, CuO + 10% ZnO, and CuO + 15% ZnO, respectively, at 1 A/g current density. Galvanostatic charge–discharge tests for these designed NCs show excellent capacitance performance in supercapacitors applications. These innovative results could be considered for expanding novel resources to scale for dual applications in photocatalysis and supercapacitors.
Citation: Inorganics
PubDate: 2023-09-16
DOI: 10.3390/inorganics11090370
Issue No: Vol. 11, No. 9 (2023)
- Inorganics, Vol. 11, Pages 371: Structural, Morphological, and Optical
Properties of Single and Mixed Ni-Co Aluminates Nanoparticles
Authors: Dana Gingasu, Ovidiu Oprea, Gabriela Marinescu, Jose Maria Calderon Moreno, Daniela C. Culita, Silviu Preda, Vasile-Adrian Surdu
First page: 371
Abstract: A series including single and mixed Ni-Co aluminates was obtained using the precursor method, with malic acid as a ligand. The malate precursors (polynuclear coordination compounds) were isolated and characterized by Fourier Transform Infrared (FTIR), Ultraviolet/Visible/Near Infrared (UV–Vis–NIR) spectroscopy, and thermal analysis. The UV–Vis–NIR spectra of the synthesized complex compounds highlighted the presence of Co2+ and Ni2+ in an octahedral environment. The thermal decomposition of these precursors led to Co1−xNixAl2O4 (x = 0, 0.1, 0.25, 0.5, 0.75, 0.9, and 1) spinels. The effect of Ni2+ substitution on the structure, morphology, and optical properties of the obtained oxides was studied with the help of different characterization tools. XRD, FTIR, and Raman spectra evidenced the formation of the spinel phase. The size of the crystallites and the agglomeration degree of the particles decrease when the nickel content increases. The band gap (BG) value is not significantly influenced by the Ni substitution. The fluorescence spectra recorded for all samples show a similar pattern, but different intensities of the emission bands.
Citation: Inorganics
PubDate: 2023-09-16
DOI: 10.3390/inorganics11090371
Issue No: Vol. 11, No. 9 (2023)
- Inorganics, Vol. 11, Pages 372: Organoruthenium Complexes Containing
Phosphinodicarboxamide Ligands
Authors: Roberto Nolla-Saltiel, Ana M. Geer, Helen R. Sharpe, Cameron D. Huke, Laurence J. Taylor, Thomas G. Linford-Wood, Ashleigh James, Jamie Allen, William Lewis, Alexander J. Blake, Jonathan McMaster, Deborah L. Kays
First page: 372
Abstract: Ruthenium complexes of phosphinocarboxamide ligands, and their use to form metallacycles using halide abstraction/deprotonation reactions are reported. Thus, [Ru(p-cym){PPh2C(=O)NHR}Cl2; R = iPr (1), Ph (2), p-tol (3)] and [Ru(p-cym){PPh2C(=O)N(R)C(=O)N(H)R}Cl2; R = Ph (4), p-tol (5)] were synthesized from [(p-cym)RuCl2]2 (p-cym = para-cymene) and phosphinocarboxamides or phosphinodicarboxamides, respectively. Single-crystal X-ray diffraction measurements on 1–5 reveal coordination to ruthenium through the phosphorus donor, with an intramolecular hydrogen bond between the amine-bound proton and a metal-bound chloride. Six-membered metallacycles formed by halide abstraction/deprotonation of complexes 4 and 5 afforded [Ru(p-cym){κ2-P,N-PPh2C(=O)N(R)C(=O)NR}Cl] [R = Ph (6), p-tol (7)]. These species exist as a mixture of two rotational isomers in solution, as demonstrated by NMR spectroscopy.
Citation: Inorganics
PubDate: 2023-09-19
DOI: 10.3390/inorganics11090372
Issue No: Vol. 11, No. 9 (2023)
- Inorganics, Vol. 11, Pages 373: The Analytical Application of Quenching
Phenomena of CdTe Quantum Dot Nanoparticles
Authors: Petra Humajová, Patrik Baliak, Ivan Landry Yumdjo Youmbissi, Alžběta Jebavá, Lenka Řezáčová, Přemysl Lubal
First page: 373
Abstract: This paper is devoted to the synthesis and application of CdTe quantum dot (QD) nanoparticles covered with organic ligands containing a thiol group, mostly mercaptopropionic acid (MPA) and glutathione (GSH). The simple one-step synthetic procedure was optimized to prepare greater quantities of nanoparticles for analytical purposes. The prepared CdTe QD nanoparticles were characterized by various analytical techniques, and their interaction with some metal ions (Cu(II), Pb(II), and Hg(II)) was studied by using luminescence spectroscopy in both steady-state and time-resolved modes. The mathematical analysis of the quenching effect of Cu(II) ions on the luminescence of CdTe QD nanoparticles shows that the static contribution is mostly responsible for the overall effect, but experimental conditions, such as pH, ionic strength, or the concentration of nanoparticles in aqueous solution, could also be important. The presence of metal ions in the form of a metal complex species could play an important role, and this phenomenon could be used to tune the selectivity of the quenching process. These findings have been utilized for the development of an analytical procedure for the detection and quantitative analysis of Cu(II) and Pb(II) ions in environmental water samples. In practice, this procedure could be easily implemented in a microplate format to increase throughput.
Citation: Inorganics
PubDate: 2023-09-19
DOI: 10.3390/inorganics11090373
Issue No: Vol. 11, No. 9 (2023)
- Inorganics, Vol. 11, Pages 374: Manganese(I) Diamine Electrocatalysts:
Electrochemical Carbon Dioxide Reduction to Carbon Monoxide
Authors: Badrinath Dhakal, Brooke A. Corbin, Alberto Sosa Parada, Jonathan G. Sakai, Emily A. Felton, Lauren T. McDonald, Anthony J. Gross, Gary S. Nichol, Greg A. N. Felton
First page: 374
Abstract: Novel organometallic complexes Mn(benzene-1,2-diamine)(CO)3Br, Mn-1, Mn(3-methylbenzene-1,2-diamine)(CO)3Br, Mn-2, and Re(benzene-1,2-diamine)(CO)3Cl, Re-1, have been synthesized and characterized by IR, UV/Vis, 1H-NMR, EA and HRMS. The structures of Mn-2 and Re-1 were confirmed by X-ray crystallography. The three novel compounds were studied for their electrocatalytic reduction of carbon dioxide to carbon monoxide using cyclic voltammetry in acetonitrile solutions. Controlled potential electrolysis was used to obtain information on faradaic yield, with product formation being confirmed by GC. Using earth-abundant manganese, compounds Mn-1 and Mn-2 display turnover frequencies of 108 s−1 and 82 s−1, respectively, amid selective production of carbon monoxide (faradaic yields ~85%), with minimal co-production of dihydrogen (<2%), and low overpotential of 0.18 V. The rhenium congener, Re-1, displays no activity as an electrocatalyst for carbon dioxide reduction under identical conditions.
Citation: Inorganics
PubDate: 2023-09-21
DOI: 10.3390/inorganics11090374
Issue No: Vol. 11, No. 9 (2023)
- Inorganics, Vol. 11, Pages 314: Binder-Free CoMn2O4 Nanoflower
Particles/Graphene/Carbon Nanotube Composite Film for a High-Performance
Lithium-Ion Battery
Authors: Xin Tong, Bo Yang, Fei Li, Manqi Gu, Xinxing Zhan, Juan Tian, Shengyun Huang, Gang Wang
First page: 314
Abstract: Manganese-based bimetallic oxides show a high theoretical specific capacity, making them a potential next-generation lithium-ion battery anode material. However, as with metal oxide anode materials, aggregation, volume expansion, and poor conductivity are the main obstacles. In this manuscript, flexible CoMn2O4/graphene/carbon nanotube films were successfully prepared through a facile filtration strategy and a subsequent thermal treatment process. When used as anodes for lithium batteries, these films can be pressed onto nickel foam without other conductive additives and binders, which simplifies the manufacturing process. When used as an anode in the lithium-ion battery, CoMn2O4/GR/CNT film exhibits a high discharge capacity of 881 mAh g−1 after 55 cycles. This value is ~2 times higher than the discharge capacity of CoMn2O4. The three-dimensional GR/CNT carrier effectively dispersed CoMn2O4, preventing its aggregation and alleviating the problem of volume expansion.
Citation: Inorganics
PubDate: 2023-07-25
DOI: 10.3390/inorganics11080314
Issue No: Vol. 11, No. 8 (2023)
- Inorganics, Vol. 11, Pages 315: Light Inorganic Scintillation Materials
for Neutron and Charge Particle Detection
Authors: Mikhail Korzhik, Ilia Komendo, Andrei Fedorov, Alexey Bondaray, Daria Kuznetsova, Vitaly Mechinsky, Andrei Vasil’ev
First page: 315
Abstract: The technological aspects of the light inorganic crystalline compounds suitable to create scintillation materials to detect charged particles and neutrons in a wide energy range have been examined. Among them, Li2CaSiO4:Eu was found to be a prospective candidate to control the valent state of the Rare Earth (RE) and to provide a high intensity of luminescence. It was demonstrated that the material has room for future improvement; however, this requires precise engineering of its composition—an experimental search of compositions or additives that will provide the maximum Eu2+/Eu3+ ratio to achieve a high scintillation light yield. The benefits of light inorganic materials are disclosed through the modeling of the linear density of nonequilibrium carriers along secondary particle tracks created in scintillators utilized for neutron detection. It is shown that oxide matrices have a larger linear density in comparison with halide crystalline compounds under alpha-particles and tritons, whereas light oxides can provide smaller numbers under protons.
Citation: Inorganics
PubDate: 2023-07-25
DOI: 10.3390/inorganics11080315
Issue No: Vol. 11, No. 8 (2023)
- Inorganics, Vol. 11, Pages 316: Superior Rate Capability of High Mass
Loading Supercapacitors Fabricated with Carbon Recovered from Methane
Cracking
Authors: Joana Baptista, Jack Shacklock, Muhammad Shaban, Anas Alkayal, Killian Lobato, Upul Wijayantha
First page: 316
Abstract: High mass loading (ca. 30 mg/cm2) electrodes were prepared with carbon recovered from catalytic methane cracking (MC). As-fabricated supercapacitors displayed 74% of capacitance retention from 6 mA/cm2 to 60 mA/cm2 and a Ragone plot’s slope of −7 Wh/kW (compared to 42% and −31 Wh/kW, respectively, for high mass loading devices fabricated with commercial carbon). The high-rate capability of the MC-recovered carbon is attributed to the presence of carbon black and carbon nanotubes produced during the reaction, which likely increased the electronic and ionic conductivity within the electrode. These results suggest that the by-product of this hydrogen generation route might be a suitable active material for supercapacitors.
Citation: Inorganics
PubDate: 2023-07-27
DOI: 10.3390/inorganics11080316
Issue No: Vol. 11, No. 8 (2023)
- Inorganics, Vol. 11, Pages 317: Photoluminescent Lanthanide(III)
Coordination Polymers with Bis(1,2,4-Triazol-1-yl)Methane Linker
Authors: Elizaveta A. Ivanova, Ksenia S. Smirnova, Ivan P. Pozdnyakov, Andrei S. Potapov, Elizaveta V. Lider
First page: 317
Abstract: A series of new lanthanide(III) coordination polymers with the general formula [Ln(btrm)2(NO3)3]n, where btrm = bis(1,2,4-triazol-1-yl)methane and Ln = Eu3+, Tb3+, Sm3+, Dy3+, Gd3+ were synthesized and characterized by IR-spectroscopy, elemental, thermogravimetric, single-crystal, and powder X-ray diffraction analyses. Europium(III), samarium(III), terbium(III), and gadolinium(III) coordination polymers demonstrate thermal stability up to 250 °C, while dysprosium(III) is stable up to 275 °C. According to single-crystal X-ray diffraction analysis, the ligand exhibits a bidentate-bridging coordination mode, forming a polymeric chain of octagonal metallocycles. The photoluminescence of the free ligand in the polycrystalline state is observed in the ultraviolet range with a quantum yield of 13%. The energy transfer from the ligand to the lanthanide ions was not observed for all obtained coordination polymers. However, there are sharp bands of lanthanide(III) ions in the diffuse reflectance and excitation spectra of the obtained compounds. Therefore, Ln(III) luminescence arises, most probably, from the enhancement of f-f transition intensity under the influence of the ligand field and non-centrosymmetric interactions.
Citation: Inorganics
PubDate: 2023-07-27
DOI: 10.3390/inorganics11080317
Issue No: Vol. 11, No. 8 (2023)
- Inorganics, Vol. 11, Pages 318: Reactivity of N-Heterocyclic Stannylenes:
Oxidative Addition of Chalcogen Elements to a Chiral NH-Sn System
Authors: Kerry R. Flanagan, James D. Parish, Gabriele Kociok-Köhn, Andrew L. Johnson
First page: 318
Abstract: The reactivity of the racemic N-heterocyclic stannylene [{MeHCN(tBu)}Sn] (1) with the chalcogenide elements O2, S, Se, and Te has been investigated. In the case of the reaction of 1 with molecular oxygen, the cyclic tristannoxane complex [{MeHCN(tBu)}2Sn(μ-O)]3 (3) was isolated and characterised. NMR studies (1H, 13C, and 119Sn) show the formation of D3- and C2- symmetric assemblies. The reaction of 1 with S, Se, and Te, respectively, yielded the cyclo-distannachalcogenide complexes, [{MeHCN(tBu)}2Sn(μ-E)]3 (4: E = S, 5: E = Se, 6: E = Te), again with multinuclear NMR studies proving the formation of C2- and Cs-symmetric assemblies. Single crystal X-ray diffraction studies have been used to elucidate the molecular structures of the products of oxidative addition, 3, 4, 5, and 6.
Citation: Inorganics
PubDate: 2023-07-27
DOI: 10.3390/inorganics11080318
Issue No: Vol. 11, No. 8 (2023)
- Inorganics, Vol. 11, Pages 319: Tailoring of Hydrogen Generation by
Hydrolysis of Magnesium Hydride in Organic Acids Solutions and Development
of Generator of the Pressurised H2 Based on this Process
Authors: Mykhaylo V. Lototskyy, Moegamat Wafeeq Davids, Tshepo Kgokane Sekgobela, Artem A. Arbuzov, Sergey A. Mozhzhukhin, Yongyang Zhu, Renheng Tang, Boris P. Tarasov
First page: 319
Abstract: Hydrolysis of light metals and hydrides can potentially be used for the generation of hydrogen on-board fuel cell vehicles, or, alternatively, for refilling their fuel tanks with H2 generated and pressurised without compressor on site, at near-ambient conditions. Implementation of this approach requires solution of several problems, including the possibility of controlling H2 release and avoiding thermal runaway. We have solved this problem by developing the apparatus for the controlled generation of pressurised H2 using hydrolysis of Mg or MgH2 in organic acid solutions. The development is based on the results of experimental studies of MgH2 hydrolysis in dilute aqueous solutions of acetic, citric, and oxalic acids. It was shown that the hydrogen yield approaches 100% with a fast hydrolysis rate when the molar ratio acid/MgH2 exceeds 0.9, 2.0, and 2.7 for the citric, oxalic, and acetic acids, respectively. In doing so, the pH of the reaction solutions after hydrolysis corresponds to 4.53, 2.11, and 4.28, accordingly, testifying to the buffer nature of the solutions “citric acid/magnesium citrate” and “acetic acid/magnesium acetate”. We also overview testing results of the developed apparatus where the process rate is effectively controlled by the control of the acid concentration in the hydrolysis reactor.
Citation: Inorganics
PubDate: 2023-07-27
DOI: 10.3390/inorganics11080319
Issue No: Vol. 11, No. 8 (2023)
- Inorganics, Vol. 11, Pages 320: Metal Complexes with Schiff Bases as
Antimicrobials and Catalysts
Authors: Iacopetta, Ceramella, Catalano, Mariconda, Giuzio, Saturnino, Longo, Sinicropi
First page: 320
Abstract: Complexes of Schiff bases (SBs) with metals are promising compounds exhibiting a broad range of applications, such as catalysts, polymers, dyes, and several biological activities, including antimicrobial, anticancer, antioxidant, antimalarial, analgesic, antiviral, antipyretic, and antidiabetic actions. Considering the crisis that the whole world is now facing against antimicrobial-resistant bacteria, in the present review, we chose to focus on the activity of SBs as antimicrobials, particularly underlying the most recent studies in this field. Finally, some interesting catalytic applications recently described for metal complexes with SBs have also been discussed.
Citation: Inorganics
PubDate: 2023-07-28
DOI: 10.3390/inorganics11080320
Issue No: Vol. 11, No. 8 (2023)
- Inorganics, Vol. 11, Pages 321: Synthesis of New Organoselenium-Based
Succinanilic and Maleanilic Derivatives and In Silico Studies as Possible
SARS-CoV-2 Main Protease Inhibitors
Authors: Saad Shaaban, Yasair S. Al-Faiyz, Ghayah M. Alsulaim, Mohamed Alaasar, Nasser Amri, Hussein Ba-Ghazal, Ahmed A. Al-Karmalawy, Aly Abdou
First page: 321
Abstract: Herein we report the synthesis of organic selenide-based maleanilic and succinanilic acids in good yields (up to 95%). Their structural identities were elucidated by spectroscopic techniques (e.g., IR, 1H- & 13C-NMR, and MS). The ADMET analysis, molecule electrostatic potential map, DFT, and frontier molecular orbital were used to study the organoselenium compounds’ pharmacokinetics, drug-likeness characteristics, geometries, and chemical and electronic properties. Moreover, a molecular docking tool was employed to investigate the organic selenides’ ability to inhibit the SARS-CoV-2 Mpro target (PDB: 7BFB). Within this context, organic selenides exhibited promising binding affinities to the SARS-CoV-2 Mpro receptor in the following order (12 > 11 > 10 > 9 > 7 > 8). Furthermore, molecular dynamics simulations were also carried out for 200 ns to evaluate the exact behavior of the most active compound (12) within the Mpro binding pocket of SARS-CoV-2 compared with its co-crystallized inhibitor (Co).
Citation: Inorganics
PubDate: 2023-07-29
DOI: 10.3390/inorganics11080321
Issue No: Vol. 11, No. 8 (2023)
- Inorganics, Vol. 11, Pages 322: Investigation of In Vitro Anticancer and
Apoptotic Potential of Biofabricated Silver Nanoparticles from Cardamine
hirsuta (L.) Leaf Extract against Caco-2 Cell Line
Authors: Halaswamy Hire Math, Kariyellappa Nagaraja Shashiraj, Raju Suresh Kumar, Muthuraj Rudrappa, Meghashyama Prabhakara Bhat, Dhanyakumara Shivapoojar Basavarajappa, Abdulrahman I. Almansour, Karthikeyan Perumal, Sreenivasa Nayaka
First page: 322
Abstract: Green nanoparticle (NPs) synthesis is eco-friendly, non-toxic, and the NPs have demonstrated improved biocompatibility for use in healthcare. This study evaluated the biogenic synthesis of AgNPs from the leaves of Cardamine hirsuta L. and their biological properties. The UV-Vis. spectra at 411 nm exhibited a distinct resonance spectrum for C-AgNPs produced from C. hirsuta L. FT-IR analysis exhibited the presence of functional groups of phyto-compounds of C. hirsuta responsible of silver salt reduction and capping agents of C-AgNPs. The microscopic-based study, such as HR-TEM analysis, showed that the particles were uniformly distributed, spherical, and ranged in size from 5.36 to 87.65 nm. EDX analysis confirmed a silver (Ag) content of 36.3% by weight, and XRD analysis exhibited the face-centred cubic (FCC) crystalline nature of C-AgNPs. DLS measured the mean particle size of 76.5 nm. The zeta potential was significant at −27.9 mV, and TGA analysis revealed that C-AgNPs had higher thermal stability. C-AgNPs demonstrated moderate antimicrobial activity against the tested pathogens. In addition, the anti-proliferative activity measured by the MTT assay on the Caco-2 cell line demonstrated decreased cell viability with increasing C-AgNPs dosage, with an IC50 concentration of 49.14 µg/mL. In addition, an Annexin-V/Propidium iodide flow cytometric study was utilized to evaluate the induction of apoptosis in cancer cells. Early and late apoptosis cell populations increased significantly compared to the untreated control. Therefore, green-synthesized C-AgNPs have significant antimicrobial and anti-proliferative abilities, making them intriguing options for future biomedical applications.
Citation: Inorganics
PubDate: 2023-07-31
DOI: 10.3390/inorganics11080322
Issue No: Vol. 11, No. 8 (2023)
- Inorganics, Vol. 11, Pages 323: TmCN@C82: Monometallic Clusterfullerene
Encapsulating a Tm3+ Ion
Authors: Huichao Zhang, Jinpeng Xin, Huaimin Jin, Wenhao Xiang, Muqing Chen, Yang-Rong Yao, Shangfeng Yang
First page: 323
Abstract: Metal cyanide clusterfullerenes (CYCFs) are formed via the encapsulation of a single metal atom and a cyanide unit inside fullerene cages, endowing them with excellent properties in various applications. In this work, we report the synthesis, isolation, and characterizations of the first cases of thulium (Tm)-based CYCFs with the popular C82 carbon cages. The structural elucidation of the two TmCN@C82 isomers was achieved via diverse analytical techniques, including mass spectrometry, Vis-NIR spectroscopy, single-crystal X-ray crystallography, and cyclic voltammetry. The crystallographic analyses unambiguously confirmed the molecular structures of the two TmCN@C82 isomers as TmCN@Cs(6)-C82 and TmCN@C2v(9)-C82. Both TmCN clusters adopt a well-established triangular configuration, with the Tm ion located on the symmetrical plane of the carbon cages. The electronic structures of both TmCN@C82 isomers adopt a Tm3+(CN)−@(C82)2− configuration, exhibiting characteristic spectral and electrochemical properties reminiscent of divalent endohedral metallofullerenes (EMFs). Intriguingly, unlike the divalent Tm2+ ion observed in the mono-metallofullerenes Tm@C2n, a higher oxidation state of Tm3+ is identified in the monometallic TmCN cluster due to bonding with the cyanide anion. This result provides valuable insight into the essential role of the non-metallic endo-units in governing the oxidation state of the metal ion and the electronic behaviors of EMFs.
Citation: Inorganics
PubDate: 2023-07-31
DOI: 10.3390/inorganics11080323
Issue No: Vol. 11, No. 8 (2023)
- Inorganics, Vol. 11, Pages 324: Oxidative, Genotoxic and Cytotoxic Damage
Potential of Novel Borenium and Borinium Compounds
Authors: Sibel Bayil Oguzkan, Hasan Turkez, Halil Ibrahim Ugras, Arzu Tatar, Adil Mardinoglu
First page: 324
Abstract: In this study, the biological properties of novel borenium and borinium compounds in terms of their oxidative, genotoxic, and cytotoxic effects were assessed on cultured human peripheral blood cells, as well as several types of cancer cells. Our results revealed that the borinium compounds yielded the best results in terms of supporting total antioxidant capacity (TAC). In fact, borenium 1, borenium 2, borenium 3, borinium 4, and borinium 5 compounds elevated TAC levels of cultured human blood cells at rates of 42.8%, 101.5%, 69.8%, 33.3%, and 49.2%, respectively. There were no statistically significant differences (p > 0.05) between the negative control and the groups treated with all borinium and borenium concentrations from the micronucleus (MN) and chromosome aberration (CA) assays, demonstrating the non-genotoxic effects. Moreover, borenium 1 (60.7% and 50.7%), borenium 2 (70.4% and 57.2%), borenium 3 (53.1% and 45.2%), borinium 4 (55.1% and 48.1%), and borinium 5 (51.0% and 36.1%) minimized the mitomycin C(MMC)-induced genotoxic damages at different rates as determined using CA and MN assays, respectively. Again, it was found that the borinium compounds exhibited higher cytotoxic activity on cancer cells when compared to borenium compounds. Consequently, in light of our in vitro findings, it was suggested that the novel borinium and borenium compounds could be used safely in pharmacology, cosmetics, and various medical fields due to their antioxidant and non-genotoxic features, as well as their cytotoxicity potential on cancer cells.
Citation: Inorganics
PubDate: 2023-07-31
DOI: 10.3390/inorganics11080324
Issue No: Vol. 11, No. 8 (2023)
- Inorganics, Vol. 11, Pages 325: Study of the Cathode Pt-Electrocatalysts
Based on Reduced Graphene Oxide with Pt-SnO2 Hetero-Clusters
Authors: Dmitry D. Spasov, Nataliya A. Ivanova, Ruslan M. Mensharapov, Matvey V. Sinyakov, Adelina A. Zasypkina, Elena V. Kukueva, Alexander L. Trigub, Elizaveta S. Kulikova, Vladimir N. Fateev
First page: 325
Abstract: A complex study of the structure, morphology, and electrochemical properties of the Pt20/SnO210/RGO electrocatalyst is presented. The advantage of the chemical synthesis of reduced graphene oxide (c-RGO) compared to thermal methods (t-RGO) is due to the formation of graphene plates with amorphous carbon black agglomerates and the chemical composition of the surface. The nature of the interaction between platinum and tin dioxide particles and a conclusion about the formation of heterostructures Pt-SnO2 with the surface interaction of lattices excluding the formation of hetero phases has been established. This achieves high dispersity during the formation of platinum particles without significant agglomeration and increases the electrochemical surface area (ESA) of platinum to 85 m2 g−1 vs. carbon black. In addition, the surface interaction of particles and the formation of hetero-clusters Pt-SnO2 can cause the improved activity and stability of the Pt20/SnO210/c-RGO electrocatalyst.
Citation: Inorganics
PubDate: 2023-07-31
DOI: 10.3390/inorganics11080325
Issue No: Vol. 11, No. 8 (2023)
- Inorganics, Vol. 11, Pages 326: PEPPSI-Type Pd(II)—NHC Complexes on
the Base of p-tert-Butylthiacalix[4]arene: Synthesis and Catalytic
Activities
Authors: Bulat Gafiatullin, Aigul Akchurina, Angelina Fedoseeva, Elza Sultanova, Daut Islamov, Konstantin Usachev, Vladimir Burilov, Svetlana Solovieva, Igor Antipin
First page: 326
Abstract: The creation of effective catalytic systems for cross-coupling reactions, reduction, etc., capable of working in water-organic or pure aqueous media is in great demand. The article presents the synthesis of NHC-palladium complexes of the PEPPSI type based on monoimidazolium derivatives of thiacalix[4]arene. The structure of the imidazolium precursors, obtained in 81–88% yields and the complexes themselves, obtained in 40–50% yields, is established using modern methods, including X-ray structural analysis and high-resolution mass spectrometry. It is shown that the obtained complex with bulk substituents near the palladium atom is not inferior to the well-known PEPPSI-type Organ’s catalyst in the catalysis of Suzuki-Miyaura coupling and is four times superior to the latter in the p-nitrophenol reduction reaction. Given the presence of free phenolic hydroxyl groups in the macrocycle, the obtained complexes are of interest for further post-modification or for immobilization on a carrier.
Citation: Inorganics
PubDate: 2023-08-01
DOI: 10.3390/inorganics11080326
Issue No: Vol. 11, No. 8 (2023)
- Inorganics, Vol. 11, Pages 327: A Series of Lanthanide Complexes with
Keggin-Type Monolacunary Phosphotungstate: Synthesis and Structural
Characterization
Authors: Vladimir S. Korenev, Taisiya S. Sukhikh, Maxim N. Sokolov
First page: 327
Abstract: The coordination of rare-earth metal ions (Ln3+) to polyoxometalates (POM) is regarded as a way of modifying and controlling their properties, such as single-molecular magnetism or luminescent behavior. The half-sandwich complexes of Ln3+ with monolacunary Keggin POMs (Ln3+/POM = 1:1) are of particular interest, since the Ln3+ retains its ability to coordinate extra ligands. Thus, the knowledge of the exact structures of 1:1 Ln/POM complexes is important for the development of reliable synthetic protocols for hybrid complexes. In this work, we isolated three 1:1 Gd3+/POM complexes of the general formula Cat4Gd(PW11O39)·xH2O (Cat = K+ or Me4N+). Complex (Me4N)2K2[Gd(H2O)2PW11O39]·5H2O (1) is polymeric, revealing a layered structural motif via bridging Gd3+ and K+ ions. Complexes (Me4N)6K2[Gd(H2O)3PW11O39]2·20H2O (2) and (Me4N)7K[Gd(H2O)3PW11O39]2·12H2O (3) are classified as dimeric; the difference between them consists of the different crystal packing of the polyoxometalates, which is induced by a variation in the cationic composition. Isostructural complexes have also been characterized for praseodymium, europium, terbium and dysprosium. The coordination number of Ln3+ (8) persists in all the compounds, while the binding mode of the POM varies, giving rise to different architectures with two or three H2O co-ligands per Ln3+. However, whatever the particular structure and exact composition, the {Ln(PW11O39)} moieties are always involved in bonding with each other with the formation either of polymeric chains or dimeric units. In water, these aggregates can dissociate with the formation of [Ln(H2O)4PW11O39]4-. This behavior must be taken into account when choosing L for the design of hybrid {Ln(L)POM} complexes.
Citation: Inorganics
PubDate: 2023-08-01
DOI: 10.3390/inorganics11080327
Issue No: Vol. 11, No. 8 (2023)
- Inorganics, Vol. 11, Pages 328: Phytochemical Substances—Mediated
Synthesis of Zinc Oxide Nanoparticles (ZnO NPS)
Authors: Fawzeeh Nayif Alharbi, Zulfa Mohamed Abaker, Suzan Zein Alabdeen Makawi
First page: 328
Abstract: Artemisia absinthium (A. absinthium) leaf extract was successfully used to create zinc oxide nanoparticles (ZnO NPs), and their properties were investigated via several techniques, including X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray (EDX), Fourier transform infrared (FTIR), and ultraviolet–visible spectroscopy (UV–Vis spectroscopy). SEM analysis confirmed the spherical and elliptical shapes of the particles. Three different zinc peaks were observed via EDX at the energies of 1, 8.7, and 9.8 keV, together with a single oxygen peak at 0.5 keV. The XRD analysis identified ZnO NPs as having a hexagonal wurtzite structure, with a particle size that decreased from 24.39 to 18.77 nm, and with an increasing surface area (BET) from 4.003 to 6.032 m2/g for the ZnO (without extract) and green ZnO NPs, respectively. The FTIR analysis confirmed the groups of molecules that were accountable for the stabilization and minimization of the ZnO NPs, which were apparent at 3400 cm. Using UV–Vis spectroscopy, the band-gap energies (Egs) for the green ZnO and ZnO (without extract) NPs were estimated, and the values were 2.65 and 2.79 eV, respectively.
Citation: Inorganics
PubDate: 2023-08-05
DOI: 10.3390/inorganics11080328
Issue No: Vol. 11, No. 8 (2023)
- Inorganics, Vol. 11, Pages 329: Influence of Ga Substitution on the Local
Structure and Luminescent Properties of Eu-Doped CaYAlO4 Phosphors
Authors: Ju Hyun Oh, Hyunwoo Kim, Mijeong Kang, Seunghun Lee
First page: 329
Abstract: Understanding the local environment of luminescent centers in phosphors serves as a blueprint for designing the luminescent properties of phosphors. Chemical substitution is a general strategy for engineering the local structure around luminescent center ions. In this study, we systematically investigate the luminescent properties of Ga-substituted Eu-doped CaYAlO4 (CYAGO:Eu) phosphors and the local structure of the Eu ions. The Ga substitution at the Al sites leads to a significant enhancement in the electric dipole transition of Eu3+ (5D0 → 7F2). The Judd–Ofelt analysis reveals that Eu3+ ions are substituted for Ca/Y, and the Ga substitution increases the asymmetricity of the local structure around the Eu ions because of the different ionic radii and electronegativities of Al and Ga. In addition, Eu2+ emission is missing regardless of the Ga substitution and post-hydrogen treatments. The present work provides deeper insight into the role of chemical substitution in oxide phosphors.
Citation: Inorganics
PubDate: 2023-08-06
DOI: 10.3390/inorganics11080329
Issue No: Vol. 11, No. 8 (2023)
- Inorganics, Vol. 11, Pages 330: Hydrogen Incorporation in RuxTi1−xO2
Mixed Oxides Promotes Total Oxidation of Propane
Authors: Wei Wang, Yu Wang, Phillip Timmer, Alexander Spriewald-Luciano, Tim Weber, Lorena Glatthaar, Yun Guo, Bernd M. Smarsly, Herbert Over
First page: 330
Abstract: A rational synthetic approach is introduced to enable hydrogen insertion into oxides by forming a solid solution of a reducible oxide with a less reducible oxide as exemplified with RuO2 and TiO2 (Ru_x, a mixture of x% RuO2 with (100−x)% TiO2). Hydrogen exposure at 250 °C to Ru_x (Ru_x_250R) results in substantial hydrogen incorporation accompanied by lattice strain that in turn induces pronounced activity variations. Here, we demonstrate that hydrogen incorporation in mixed oxides promotes the oxidation catalysis of propane combustion with Ru_60_250R being the catalytically most active catalyst.
Citation: Inorganics
PubDate: 2023-08-07
DOI: 10.3390/inorganics11080330
Issue No: Vol. 11, No. 8 (2023)
- Inorganics, Vol. 11, Pages 331: Copper(II) and Platinum(II) Naproxenates:
Insights on Synthesis, Characterization and Evaluation of Their
Antiproliferative Activities
Authors: Amanda A. Silva, Silmara C. L. Frajácomo, Állefe B. Cruz, Kaio Eduardo Buglio, Daniele Daiane Affonso, Marcelo Cecconi Portes, Ana Lúcia T. G. Ruiz, João Ernesto de Carvalho, Wilton R. Lustri, Douglas H. Pereira, Ana M. da Costa Ferreira, Pedro P. Corbi
First page: 331
Abstract: The growth of antibiotic resistance is a matter of worldwide concern. In parallel, cancer remains one of the main causes of death. In the search for new and improved antiproliferative agents, one of the strategies is the combination of bioactive ligands and metals that are already consolidated in the synthesis of metallopharmaceutical agents. Thus, this work deals with the synthesis, characterization, and study of naproxen (Nap)-based complexes of copper(II) and platinum(II) as antiproliferative agents. The copper complex (Cu–Nap) presents a binuclear paddle-wheel structure in a 1 Cu:2 Nap:1 H2O molar composition, in which Cu(II) is bonded to the carboxylate oxygens from naproxenate in a bidentate bridging mode. The platinum complex (Pt–Nap) was identified as the square planar cis-[Pt(Nap)2(DMSO)2] isomer, in which Pt(II) is bonded to the carboxylate oxygen atom of Nap in a monodentate fashion. Both complexes were inactive against the Gram-positive and Gram-negative bacterial strains assessed. Pt–Nap presented low cytostatic behavior over a set of tumor cells, but good viability for normal cells, while Cu–Nap was cytotoxic against all cells, with a cytocidal activity against glioma tumor cells.
Citation: Inorganics
PubDate: 2023-08-10
DOI: 10.3390/inorganics11080331
Issue No: Vol. 11, No. 8 (2023)
- Inorganics, Vol. 11, Pages 332: Symmetrical and Unsymmetrical Dicopper
Complexes Based on Bis-Oxazoline Units: Synthesis, Spectroscopic
Properties and Reactivity
Authors: James A. Isaac, Gisèle Gellon, Florian Molton, Christian Philouze, Nicolas Le Poul, Catherine Belle, Aurore Thibon-Pourret
First page: 332
Abstract: Copper–oxygen adducts are known for being key active species for the oxidation of C–H bonds in copper enzymes and their synthetic models. In this work, the synthesis and spectroscopic characterizations of such intermediates using dinucleating ligands based on a 1,8 naphthyridine spacer with oxazolines or mixed pyridine-oxazoline coordination moieties as binding pockets for copper ions have been explored. On the one hand, the reaction of dicopper(I) complexes with O2 at low temperature led to the formation of a µ-η2:η2 Cu2:O2 peroxido species according to UV-Vis spectroscopy monitoring. The reaction of these species with 2,4-di-tert-butyl-phenolate resulted in the formation of the C–C coupling product, but no insertion of oxygen occurred. On the other hand, the synthesis of dinuclear Cu(II) bis-µ-hydroxido complexes based on pyridine–oxazoline and oxazoline ligands were carried out to further generate CuIICuIII oxygen species. For both complexes, a reversible monoelectronic oxidation was detected via cyclic voltammetry at E1/2 = 1.27 and 1.09 V vs. Fc+/Fc, respectively. Electron paramagnetic resonance spectroscopy (EPR) and UV-Vis spectroelectrochemical methods indicated the formation of a mixed-valent CuIICuIII species. Although no reactivity towards exogeneous substrates (toluene) could be observed, the CuIICuIII complexes were shown to be able to perform hydroxylation on the methyl group of the oxazoline moieties. The present study therefore indicates that the electrochemically generated CuIICuIII species described herein are capable of intramolecular aliphatic oxidation of C–H bonds.
Citation: Inorganics
PubDate: 2023-08-11
DOI: 10.3390/inorganics11080332
Issue No: Vol. 11, No. 8 (2023)
- Inorganics, Vol. 11, Pages 333: Efficient Disposal of Rhodamine 6G and
Acid Orange 10 Dyes from Aqueous Media Using ZrO2/CdMn2O4/CdO as Novel and
Facilely Synthesized Nanocomposites
Authors: Ehab A. Abdelrahman, Faisal K. Algethami, Huda S. AlSalem, Mona S. Binkadem, Mohamed Khairy, Fawaz A. Saad, Gharieb S. El-Sayyad, Zahrah Alqahtani
First page: 333
Abstract: It is essential to remove rhodamine 6G and acid orange 10 dyes from contaminated water because they can induce cancer and irritate the lungs, skin, mucous, membranes, and eyes. Hence, in the current work, the Pechini sol–gel method was used for the facile synthesis of ZrO2/CdMn2O4/CdO as novel nanocomposites at 600 and 800 °C. The synthesized nanocomposites were used as novel adsorbents for the efficient removal of rhodamine 6G and acid orange 10 dyes from aqueous media. The nanocomposites, which were synthesized at 600 and 800 °C, were abbreviated as EK600 and EK800, respectively. The synthesized nanocomposites were characterized by EDS, XRD, N2 adsorption/desorption analyzer, and FE-SEM. The patterns of XRD showed that the average crystal size of the EK600 and EK800 nanocomposites is 68.25 and 85.32 nm, respectively. Additionally, the images of FE-SEM showed that the surface of the EK600 nanocomposite consists of spherical, polyhedral, and rod shapes with an average grain size of 99.36 nm. Additionally, the surface of the EK800 nanocomposite consists of polyhedral and spherical shapes with an average grain size of 143.23 nm. In addition, the BET surface area of the EK600 and EK800 nanocomposites is 46.33 and 38.49 m2/g, respectively. The optimal conditions to achieve the highest removal of rhodamine 6G and acid orange 10 dyes are pH = 8, contact time = 24 min, and temperature = 298 kelvin. The greatest removal capacity of the EK600 and EK800 adsorbents towards rhodamine 6G dye is 311.53 and 250.63 mg/g, respectively. Additionally, the greatest removal capacity of the EK600 and EK800 adsorbents towards acid orange 10 dye is 335.57 and 270.27 mg/g, respectively. The removal of rhodamine 6G and acid orange 10 dyes using the EK600 and EK800 adsorbents is spontaneous, exothermic, follows the Langmuir adsorption isotherm, and fits well with the pseudo-first-order kinetic model.
Citation: Inorganics
PubDate: 2023-08-12
DOI: 10.3390/inorganics11080333
Issue No: Vol. 11, No. 8 (2023)
- Inorganics, Vol. 11, Pages 334: Circular Dichroism Spectroscopic Studies
on Solution Chemistry of M(II)-Monensinates in Their Competition Reactions
Authors: Máté Levente Kis, Bálint Hajdu, Petar Dorkov, Ivayla Pantcheva, Béla Gyurcsik
First page: 334
Abstract: The chirality of the polyether ionophore monensic acid A can be successfully used to study its coordination ability in solution. A complementary approach to gain new insights into the complexation chemistry of the antibiotic (studied previously by circular dichroism (CD) spectroscopy in the ultraviolet range (UV-CD)) is presented. (1) Methods: The CD spectroscopy in the visible (VIS-CD) and near-infrared (NIR-CD) range is applied to evaluate the affinity of deprotonated monensic acid A (monensinate A) towards Ni(II) or Co(II) cations in methanolic solution. Competition experiments between a variety of colorless divalent metal ions for binding the ligand anion were also performed. (2) Results: The stability constants of the species observed in binary Ni(II)/Co(II)-monensinate systems and their distribution were reevaluated with the VIS- and NIR-CD techniques. The data confirmed the formation of mono and bis complexes depending on the metal-to-ligand molar ratio. The studies on the systems containing two competing divalent metal cations exclude the formation of ternary complex species but provide an opportunity to also calculate the stability constants of Zn(II), Mg(II), and Ca(II) monensinates. (3) Conclusions: The advantages of CD spectroscopy in the VIS-NIR range (“invisible” ligand and metal salts, “visible” chiral complex species) simplify the experimental dataset evaluation and increase the reliability of computed results.
Citation: Inorganics
PubDate: 2023-08-13
DOI: 10.3390/inorganics11080334
Issue No: Vol. 11, No. 8 (2023)
- Inorganics, Vol. 11, Pages 335: Matching Polynomial-Based Similarity
Matrices and Descriptors for Isomers of Fullerenes
Authors: Krishnan Balasubramanian
First page: 335
Abstract: I have computed the matching polynomials of a number of isomers of fullerenes of various sizes with the objective of developing molecular descriptors and similarity measures for isomers of fullerenes on the basis of their matching polynomials. Two novel matching polynomial-based topological descriptors are developed, and they are demonstrated to have the discriminating power to contrast a number of closely related isomers of fullerenes. The number of ways to place up to seven disjoint dimers on fullerene isomers are shown to be identical, as they are not structure-dependent. Moreover, similarity matrices that provide quantitative similarity measures among a given set of isomers of fullerenes are developed from their matching polynomials and are shown to provide robust quantitative measures of similarity.
Citation: Inorganics
PubDate: 2023-08-13
DOI: 10.3390/inorganics11080335
Issue No: Vol. 11, No. 8 (2023)
- Inorganics, Vol. 11, Pages 336: Sn(IV)porphyrin-Anchored TiO2
Nanoparticles via Axial-Ligand Coordination for Enhancement of Visible
Light-Activated Photocatalytic Degradation
Authors: Nirmal Kumar Shee, Hee-Joon Kim
First page: 336
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 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.
Citation: Inorganics
PubDate: 2023-08-15
DOI: 10.3390/inorganics11080336
Issue No: Vol. 11, No. 8 (2023)
- Inorganics, Vol. 11, Pages 337: Research and Application Progress of
Inverse Opal Photonic Crystals in Photocatalysis
Authors: Hongming Xiang, Shu Yang, Emon Talukder, Chenyan Huang, Kaikai Chen
First page: 337
Abstract: In order to solve the problem of low photocatalytic efficiency in photocatalytic products, researchers proposed a method to use inverse opal photonic crystal structure in photocatalytic materials. This is due to a large specific surface area and a variety of optical properties of the inverse opal photonic crystal, which are great advantages in photocatalytic performance. In this paper, the photocatalytic principle and preparation methods of three-dimensional inverse opal photonic crystals are introduced, including the preparation of basic inverse opal photonic crystals and the photocatalytic modification of inverse opal photonic crystals, and then the application progresses of inverse opal photonic crystal photocatalyst in sewage purification, production of clean energy and waste gas treatment are introduced.
Citation: Inorganics
PubDate: 2023-08-15
DOI: 10.3390/inorganics11080337
Issue No: Vol. 11, No. 8 (2023)
- Inorganics, Vol. 11, Pages 338: Heterotridentate Organomonophosphines in
Pt(η3-P1C1C2)(Y) and Pt(η3-P1C1N1)(Y) Derivatives—Structural
Aspects
Authors: Milan Melník, Veronika Mikušová, Peter Mikuš
First page: 338
Abstract: This paper covers Pt(II) complexes of the compositions Pt(η3-P1C1C2)(Y) (Y = NL or I) and Pt(η3-P1C1N1)(Y), Y = OL, NL, CL, Cl or Br). These complexes crystallized in four crystal classes: monoclinic (9 examples), triclinic (3 examples), orthorhombic (3 examples), and tetragonal (2 examples). The structural parameters (Pt-L, L-Pt-L) are analyzed and discussed with attention to the distortion of square-planar geometry about the Pt(II) atoms and trans-influence. These data are compared and discussed with those of Pt(η3-P1N1N2)(Y), Pt(η3-P1N1X1)(Y), (X1=O1, C1, S1, Se1), Pt(η3-N1P1N2)(Cl), Pt(η3-S1P1S2)(Cl), Pt(η3-P1S1Cl1)(Cl), and Pt(η3-P1Si1N1)(OL) types. Each heterotridentate ligand creates two metallocyclic rings with a common central ligating atom. These η3-ligands form twenty-three types of metallocycles and differ by the number and type of the atoms involved in the metallocyclic rings.
Citation: Inorganics
PubDate: 2023-08-16
DOI: 10.3390/inorganics11080338
Issue No: Vol. 11, No. 8 (2023)
- Inorganics, Vol. 11, Pages 339: Facile Synthesis and Characterization of
Novel Nanostructures for the Efficient Disposal of Crystal Violet Dye from
Aqueous Media
Authors: Ehab A. Abdelrahman, Faisal K. Algethami, Huda S. AlSalem, Mona S. Binkadem, Fawaz A. Saad, Gharieb S. El-Sayyad, Nadeem Raza, Khalil ur Rehman
First page: 339
Abstract: An excessive accumulation of crystal violet dye in the human body results in an accelerated heart rate, tetraplegia, eye irritation, and long-term damage to the transparent mucous membrane that protects the eyeballs. Accordingly, in this paper, sodium manganese silicate/sodium manganese silicate hydroxide hydrate was easily fabricated as a novel type of nanostructures for the successful disposal of crystal violet dye from aqueous solutions. The formed sodium manganese silicate/sodium manganese silicate hydroxide hydrate nanostructures after the hydrothermal treatment of the gel produced from the interaction of Mn(II) ions with Si(IV) ions at 180 °C for 6, 12, 18, and 24 h were abbreviated as MS1, MS2, MS3, and MS4, respectively. The XRD showed that the average crystallite size of the MS1, MS2, MS3, and MS4 samples is 8.38, 7.43, 4.25, and 8.76 nm, respectively. The BET surface area of the MS1, MS2, MS3, and MS4 samples is 41.58, 46.15, 58.25, and 39.69 m2/g, respectively. The MS1, MS2, MS3, and MS4 samples consist of spherical and irregular shapes with average grain sizes of 157.22, 88.06, 43.75, and 107.08 nm, respectively. The best adsorption conditions of the crystal violet dye employing the MS1, MS2, MS3, and MS4 products were achieved at pH = 8, contact time = 140 min, and solution temperature = 298 kelvin. The linear pseudo-2nd-order model as well as the linear Langmuir isotherm better describe the disposal of the crystal violet dye using the MS1, MS2, MS3, and MS4 adsorbents. The studied thermodynamic parameters indicated that the disposal of the crystal violet dye employing the MS1, MS2, MS3, and MS4 adsorbents is spontaneous, exothermic, and chemical. The maximum disposal capacities of the MS1, MS2, MS3, and MS4 adsorbents towards crystal violet dye are 342.47, 362.32, 411.52, and 310.56 mg/g, respectively.
Citation: Inorganics
PubDate: 2023-08-17
DOI: 10.3390/inorganics11080339
Issue No: Vol. 11, No. 8 (2023)
- Inorganics, Vol. 11, Pages 340: Correction: Tian et al. Fluorescence
Resonance Energy Transfer Properties and Auger Recombination Suppression
in Supraparticles Self-Assembled from Colloidal Quantum Dots. Inorganics
2023, 11, 218
Authors: Xinhua Tian, Hao Chang, Hongxing Dong, Chi Zhang, Long Zhang
First page: 340
Abstract: Error in Figure [...]
Citation: Inorganics
PubDate: 2023-08-18
DOI: 10.3390/inorganics11080340
Issue No: Vol. 11, No. 8 (2023)
- Inorganics, Vol. 11, Pages 341: Significantly Enhanced Self-Cleaning
Capability in Anatase TiO2 for the Bleaching of Organic Dyes and Glazes
Authors: Tiangui Zhao, Tihao Cao, Qifu Bao, Weixia Dong, Ping Li, Xingyong Gu, Yunzi Liang, Jianer Zhou
First page: 341
Abstract: In this study, the Mg2+-doped anatase TiO2 phase was synthesized via the solvothermal method by changing the ratio of deionized water and absolute ethanol Vwater/Vethanol). This enhances the bleaching efficiency under visible light. The crystal structure, morphology, and photocatalytic properties of Mg-doped TiO2 were characterized by X-ray diffraction, scanning electron microscopy, high-resolution transmission electron microscopy, N2 adsorption-desorption, UV-Vis spectroscopy analysis, etc. Results showed that the photocatalytic activity of the Mg2+-doped TiO2 sample was effectively improved, and the morphology, specific surface area, and porosity of TiO2 could be controlled by Vwater/Vethanol. Compared with the Mg-undoped TiO2 sample, Mg-doped TiO2 samples have higher photocatalytic properties due to pure anatase phase formation. The Mg-doped TiO2 sample was synthesized at Vwater/Vethanol of 12.5:2.5, which has the highest bleaching rate of 99.5% for the rhodamine B dye during 80 min under visible light. Adding Mg2+-doped TiO2 into the phase-separated glaze is an essential factor for enhancing the self-cleaning capability. The glaze samples fired at 1180 °C achieved a water contact angle of 5.623° at room temperature and had high stain resistance (the blot floats as a whole after meeting the water).
Citation: Inorganics
PubDate: 2023-08-18
DOI: 10.3390/inorganics11080341
Issue No: Vol. 11, No. 8 (2023)
- Inorganics, Vol. 11, Pages 342: In Situ Preparation of 2D Co-B
Nanosheets@1D TiO2 Nanofibers as a Catalyst for Hydrogen Production from
Sodium Borohydride
Authors: Ibrahim M. Maafa, Nasser Zouli, Ahmed Abutaleb, Ayman Yousef, Isam Y. Qudsieh, Saleh M. Matar, Abdel Samed M. Adam, M. M. El-Halwany
First page: 342
Abstract: In this study, 2D Co-B nanosheet-decorated 1D TiO2 nanofibers (2D Co-B NS-decorated 1D TiO2 NFs) are synthesized via electrospinning and an in situ chemical reduction technique. The as-prepared catalyst showed excellent catalytic performance in H2 generation from sodium borohydride (SBH). When compared to naked Co-B nanoparticles, the catalytic activity of the 2D Co-B NS-decorated 1D TiO2 NFs catalyst for the hydrolysis of SBH is significantly enhanced, as demonstrated by the high hydrogen generation rate (HGR) of 6020 mL min−1 g−1 at 25 °C. The activation energy of hydrolysis was measured to be 30.87 kJ mol−1, which agreed with the reported values. The catalyst also showed good stability. Moreover, the effects of SBH, catalyst concentration, and temperature on the catalytic performance of 2D Co-B NS-decorated 1D TiO2 NFs were studied to gain a comprehensive understanding of the dehydrogenation mechanism of SBH. Based on these findings, we conclude that 2D Co-B NS-decorated 1D TiO2 NFs are effective catalytic materials for the dehydrogenation of SBH.
Citation: Inorganics
PubDate: 2023-08-18
DOI: 10.3390/inorganics11080342
Issue No: Vol. 11, No. 8 (2023)
- Inorganics, Vol. 11, Pages 343: Synthesis of Polystyrene@TiO2
Core–Shell Particles and Their Photocatalytic Activity for the
Decomposition of Methylene Blue
Authors: Naoki Toyama, Tatsuya Takahashi, Norifumi Terui, Shigeki Furukawa
First page: 343
Abstract: In this study, we investigated the preparation conditions of polystyrene (PS)@TiO2 core–shell particles and their photocatalytic activity during the decomposition of methylene blue (MB). TiO2 shells were formed on the surfaces of PS particles using the sol–gel method. Homogeneous PS@TiO2 core–shell particles were obtained using an aqueous NH3 solution as the promoter of the sol–gel reaction and stirred at room temperature. This investigation revealed that the temperature and amount of the sol–gel reaction promoter influenced the morphology of the PS@TiO2 core–shell particles. The TiO2 shell thickness of the PS@TiO2 core–shell particles was approximately 5 nm, as observed using transmission electron microscopy. Additionally, Ti elements were detected on the surfaces of the PS@TiO2 core–shell particles using energy-dispersive X-ray spectroscopy analysis. The PS@TiO2 core–shell particles were used in MB decomposition to evaluate their photocatalytic activities. For comparison, we utilized commercial P25 and TiO2 particles prepared using the sol–gel method. The results showed that the PS@TiO2 core–shell particles exhibited higher activity than that of the compared samples.
Citation: Inorganics
PubDate: 2023-08-21
DOI: 10.3390/inorganics11080343
Issue No: Vol. 11, No. 8 (2023)
- Inorganics, Vol. 11, Pages 344: QSPR and Nano-QSPR: Which One Is Common'
The Case of Fullerenes Solubility
Authors: Alla P. Toropova, Andrey A. Toropov, Natalja Fjodorova
First page: 344
Abstract: Background: The system of self-consistent models is an attempt to develop a tool to assess the predictive potential of various approaches by considering a group of random distributions of available data into training and validation sets. Considering many different splits is more informative than considering a single model. Methods: Models studied here build up for solubility of fullerenes C60 and C70 in different organic solvents using so-called quasi-SMILES, which contain traditional simplified molecular input-line entry systems (SMILES) incorporated with codes that reflect the presence of C60 and C70. In addition, the fragments of local symmetry (FLS) in quasi-SMILES are applied to improve the solubility’s predictive potential (expressed via mole fraction at 298’K) models. Results: Several versions of the Monte Carlo procedure are studied. The use of the fragments of local symmetry along with a special vector of the ideality of correlation improves the predictive potential of the models. The average value of the determination coefficient on the validation sets is equal to 0.9255 ± 0.0163. Conclusions: The comparison of different manners of the Monte Carlo optimization of the correlation weights has shown that the best predictive potential was observed for models where both fragments of local symmetry and the vector of the ideality of correlation were applied.
Citation: Inorganics
PubDate: 2023-08-21
DOI: 10.3390/inorganics11080344
Issue No: Vol. 11, No. 8 (2023)
- Inorganics, Vol. 11, Pages 345: Physicochemical Fundamentals of the
Synthesis of a Cu@BN Composite Consisting of Nanosized Copper Enclosed in
a Boron Nitride Matrix
Authors: Elena A. Malinina, Ivan I. Myshletsov, Grigorii A. Buzanov, Irina V. Kozerozhets, Nikolay P. Simonenko, Tatiana L. Simonenko, Svetlana E. Nikiforova, Varvara V. Avdeeva, Konstantin Yu. Zhizhin, Nikolay T. Kuznetsov
First page: 345
Abstract: The thermal reduction of the copper(II) complexes [CuII(N2H4)3][B10H10]·nH2O (I·nH2O) and [CuII(NH3)4][B10H10]·nH2O (II·nH2O) has been studied in an argon atmosphere at 900 °C. It has been found that the annealing of both compounds results in a Cu@BN boron-containing copper composite. It has been shown that this process leads to the formation of a boron nitride matrix doped with cubic copper(0) nanoparticles due to the copper(II)→copper(I)→copper(0) thermal reduction. The phase composition of annealing products I900 and II900 has been determined based on powder X-ray diffraction, IR spectroscopy and thermal analysis data. The morphology, average particle size and composition of the composite have been determined by TEM and high-resolution TEM + EDS. The average particle size has been found to be about 81 nm and 52 nm for samples I900 and II900, respectively. Comparison of the results obtained using physicochemical studies has shown the identity of the composition of the products of annealing I900 and II900. The electrical properties of a coating based on an I900 sample modified with Cu0→Cu2O in situ during deposition on a chip at 300 °C in air have been studied. As a result, with increasing temperature, an increase in the electrical conductivity characteristic of semiconductors has been observed.
Citation: Inorganics
PubDate: 2023-08-21
DOI: 10.3390/inorganics11080345
Issue No: Vol. 11, No. 8 (2023)
- Inorganics, Vol. 11, Pages 346: Recent Progress on the Functionalization
of Endohedral Metallofullerenes
Authors: Song Wang, Xianming Zhang, Xi Tan, Hongzhen Li, Songxin Dai, Bin Yao, Xingyan Liu, Youzhou He, Fei Jin
First page: 346
Abstract: Functionalization of endohedral metallofullerenes (EMFs) plays an important role in exploring the reactivity of EMFs and stabilizing missing EMFs, thus conferring tunable properties and turning EMFs into applicable materials. In this review, we present exhaustive progress on the functionalization of EMFs since 2019. Classic functionalization reactions include Prato reactions, Bingel–Hirsch reactions, radical addition reactions, carbene addition reactions, and so on are summarized. And new complicated multi-component reactions and other creative reactions are presented as well. We also discuss the structural features of derivatives of EMFs and the corresponding reaction mechanisms to understand the reactivity and regioselectivity of EMFs. In the end, we make conclusions and put forward an outlook on the prospect of the functionalization of EMFs.
Citation: Inorganics
PubDate: 2023-08-21
DOI: 10.3390/inorganics11080346
Issue No: Vol. 11, No. 8 (2023)
- Inorganics, Vol. 11, Pages 287: Elemental Selenium in the Synthesis of
Selenaheterocycles
Authors: Alexander V. Martynov
First page: 287
Abstract: An overview of the known methods of introducing selenium under the action of elemental selenium into the structures of various saturated, unsaturated, and heteroaromatic selenacycles containing C–Se, N–Se, B–Se, Ge–Se and P–Se bonds is presented. These methods include metal, iodine, bromine or chlorine exchange for selenium and the direct cyclization of 1-(2-bromoaryl)benzimidazoles, polyunsaturated hydrocarbons, acetylenes, propargylic amines, 3-halogenaryl amides, aryl amides, diazo-compounds, 2-aminoacetophenone, and the annulation of ethynyl arenes. Three- and four-component reactions utilizing elemental selenium as one of the components and leading to selenium-containing heterocycles are presented as well.
Citation: Inorganics
PubDate: 2023-07-02
DOI: 10.3390/inorganics11070287
Issue No: Vol. 11, No. 7 (2023)
- Inorganics, Vol. 11, Pages 288: Phase Formation of Co and Cr Co-Doped
Bismuth Niobate with Pyrochlore Structure
Authors: Nadezhda A. Zhuk, Ksenia A. Badanina, Roman I. Korolev, Boris A. Makeev, Maria G. Krzhizhanovskaya, Vladislav V. Kharton
First page: 288
Abstract: The formation mechanisms of pyrochlore-type Bi2Co1/2Cr1/2Nb2O9+Δ (space group Fd-3m, a = 10.4838(8) Å), in the temperature range from 400 to 1050 °C were studied by employing X-ray diffraction, scanning electron microscopy and energy-dispersive spectroscopy. An extensive reaction between the binary metal oxides was found to begin at temperatures above 550 °C, following the transition of monoclinic α-Bi2O3 into a tetragonal β-Bi2O3 polymorph. The synthesis process occurs in several stages when Bi-rich intermediate products (Bi6CrO12, Bi6Cr2O15, and Bi5Nb3O15) transform into bismuth-depleted BiNbO4 and a chromium–cobalt spinel is formed. The formation of a single pyrochlore phase occurs at the final reaction stage at 1050 °C via the doping of bismuth ortho-niobate, BiNbO4, by the transition metal cations. The observed mechanism is essentially similar to the mechanism of tantalate-based phases except for the formation of Bi5Nb3O15 at the intermediate reaction stages.
Citation: Inorganics
PubDate: 2023-07-03
DOI: 10.3390/inorganics11070288
Issue No: Vol. 11, No. 7 (2023)
- Inorganics, Vol. 11, Pages 289: Recent Advances in Anode Materials for
Sodium-Ion Batteries
Authors: Xue Bai, Nannan Wu, Gengchen Yu, Tao Li
First page: 289
Abstract: Although lithium-ion battery (LIB) technology has prevailed for years, the growing pressure and increased cost of lithium sources urge the rapid development of other promising energy storage devices. As a low-cost alternative, sodium-ion batteries (SIBs) with similar properties of electrochemical reaction have caught researchers’ attention. Nevertheless, great challenges of inferior reversible capacity and poor lifespan induced by the bigger ionic radius of sodium ions still exist. To solve these problems, improvements to anode materials prove to be an effective way. Herein, the latest research on promising anodes in SIBs is summarized, and the further prospects are also illustrated.
Citation: Inorganics
PubDate: 2023-07-06
DOI: 10.3390/inorganics11070289
Issue No: Vol. 11, No. 7 (2023)
- Inorganics, Vol. 11, Pages 290: Metal Hydride Hydrogen Storage
Authors: Boris Tarasov, Artem Arbuzov, Sergey Mozhzhukhin, Aleksey Volodin, Pavel Fursikov, Moegamat Wafeeq Davids, Joshua Adeniran, Mykhaylo Lototskyy
First page: 290
Abstract: Metal hydride (MH) hydrogen storage and compression systems with near-atmospheric H2 suction pressure are necessary for the utilization of the low-pressure H2 produced by solid oxide electrolyzers or released as a byproduct of chemical industries. Such systems should provide reasonably high productivity in the modes of both charge (H2 absorption at PL ≤ 1 atm) and discharge (H2 desorption at PH = 2–5 atm), which implies the provision of H2 equilibrium pressures Peq < PL at the available cooling temperature (TL = 15–20 °C) and, at the same time, Peq > PH when heated to TH = 90–150 °C. This work presents results of the development of such systems based on AB5-type intermetallics characterized by Peq of 0.1–0.3 atm and 3–8 atm for H2 absorption at TL = 15 °C and H2 desorption at TH = 100 °C, respectively. The MH powders mixed with 1 wt.% of Ni-doped graphene-like material or expanded natural graphite for the improvement of H2 charge dynamics were loaded in a cylindrical container equipped with internal and external heat exchangers. The developed units with a capacity of about 1 Nm3 H2 were shown to exhibit H2 flow rates above 10 NL/min during H2 charge at ≤1 atm when cooled to ≤20 °C with cold water and H2 release at a pressure above 2 and 5 atm when heated to 90 and 120 °C with hot water and steam, respectively.
Citation: Inorganics
PubDate: 2023-07-06
DOI: 10.3390/inorganics11070290
Issue No: Vol. 11, No. 7 (2023)
- Inorganics, Vol. 11, Pages 291: Synthesis, Luminescence and Energy
Transfer Properties of Ce3+/Mn2+ Co-Doped Calcium Carbodiimide Phosphors
Authors: Erwan Leysour de Rohello, Yan Suffren, Francis Gouttefangeas, Odile Merdrignac-Conanec, Olivier Guillou, François Cheviré
First page: 291
Abstract: Ce3+-doped and Ce3+/Mn2+ co-doped calcium carbodiimide (CaCN2) phosphors were synthesized from doped calcium carbonate and carbon nitride by a solid-state reaction at 700 °C under flowing NH3 using a very short reaction time (1 h). The samples were characterized by powder X-ray diffraction, scanning electron microscopy and their diffuse reflectance and luminescence properties were investigated. Single-doped CaCN2:Ce3+ exhibits a blue emission under near-ultraviolet activation (386 nm) corresponding to the 5d1 → 2F5/2 and 5d1 → 2F7/2 transitions of Ce3+. Maximum emission is obtained at temperatures lower than 150 K and then progressively decreases up to 387 K, with an 80% drop in the emission at room temperature. Efficient energy transfers from Ce3+ to Mn2+ via a non-radiative dipole–dipole mechanism are evidenced for the co-doped samples, leading to various colored phosphors under near-ultraviolet activation (386 nm). The emission color of the obtained phosphors can be modulated from blue to red through a shade of white depending on the sensitizer/activator ratio.
Citation: Inorganics
PubDate: 2023-07-07
DOI: 10.3390/inorganics11070291
Issue No: Vol. 11, No. 7 (2023)
- Inorganics, Vol. 11, Pages 292: Green Synthesis of MIL-88B(Cr) with the
Co-Modulator of Nitric Acid and Acetic Acid
Authors: Fuzhi Li, Songfan Tang, Mingmin Li, Pengcheng Xiao, Mingliang Luo, Tian Zhao
First page: 292
Abstract: MIL-88B(Cr) is a prototypical flexible chromium-based metal-organic framework (MOF), which possesses extremely strong water/thermal stability and excellent “swelling/breathing” ability. However, in previous studies, there have been very few reports on MIL-88B(Cr) due to unclear synthesis details. Here, we found that the pure MIL-88B(Cr) can be facile synthesized through a hydrothermal method with the co-use of nitric acid and acetic acid (molar ratio = 1:15). The obtained MIL-88B(Cr) was sufficiently characterized by diverse techniques to assure its high-level quality. This work emphasizes a future valuable approach to expanding the production of flexible Cr-based MOF.
Citation: Inorganics
PubDate: 2023-07-11
DOI: 10.3390/inorganics11070292
Issue No: Vol. 11, No. 7 (2023)
- Inorganics, Vol. 11, Pages 293: Benzimidazole-Based NHC Metal Complexes as
Anticancer Drug Candidates: Gold(I) vs. Platinum(II)
Authors: Paul Kapitza, Patricia Grabher, Amelie Scherfler, Klaus Wurst, Brigitte Kircher, Ronald Gust, Hristo P. Varbanov
First page: 293
Abstract: Herein, we present a comparative study on the chemistry and biological activity of N-heterocyclic carbene (NHC)Pt(II)/Au(I) complexes. Accordingly, representative compounds of the cis/trans- [PtL2X2] (X = Cl (5, 6) or I (7, 8)), [PtL3Cl]+ (9), [AuLX] (X = Cl (10) or I (11)), and [AuL2]+ (12) type, where L is 1,3-diethylbenzimidazol-2-ylidene, were synthesized and characterized in detail to elucidate the role of the metal center on their physicochemical and biological properties. The stability of the complexes in the presence of cell culture medium and their reactivity toward relevant biomolecules were investigated by RP-HPLC. In addition, their effects on plasmid DNA and in vitro cytotoxicity in ovarian cancer cells and non-malignant fibroblasts were evaluated. Cationic [AuL2]+ and [PtL3X]+ species displayed the highest cytotoxicity and stability in cell culture medium in the series. They exhibited IC50 values lower than the established metallodrugs cisplatin and auranofin in both wild-type and cisplatin-resistant ovarian cancer cells, being able to circumvent cisplatin resistance. Finally, Pt(II)–NHC complexes form 5′-guanosine monophosphate adducts under physiologically relevant conditions and interact with plasmid DNA in contrast to their Au(I) analogs, corroborating their distinct modes of action.
Citation: Inorganics
PubDate: 2023-07-11
DOI: 10.3390/inorganics11070293
Issue No: Vol. 11, No. 7 (2023)
- Inorganics, Vol. 11, Pages 294: Nanomaterials Used in the Preparation of
Personal Protective Equipment (PPE) in the Fight against SARS-CoV-2
Authors: Pierantonio De Luca, Janos B.Nagy, Anastasia Macario
First page: 294
Abstract: Following the well-known pandemic, declared on 30 January 2020 by the World Health Organization, the request for new global strategies for the prevention and mitigation of the spread of the infection has come to the attention of the scientific community. Nanotechnology has often managed to provide solutions, effective responses, and valid strategies to support the fight against SARS-CoV-2. This work reports a collection of information on nanomaterials that have been used to counter the spread of the SARS-CoV-2 virus. In particular, the objective of this work was to illustrate the strategies that have made it possible to use the particular properties of nanomaterials, for the production of personal protective equipment (DIP) for the defense against the SARS-CoV-2 virus.
Citation: Inorganics
PubDate: 2023-07-12
DOI: 10.3390/inorganics11070294
Issue No: Vol. 11, No. 7 (2023)
- Inorganics, Vol. 11, Pages 295: Complexation of Boron and Aluminum with a
Bidentate Hydroxy-BN-naphthalene Ligand
Authors: Yannik Appiarius, Pim Puylaert, Julius Werthschütz, Tim Neudecker, Anne Staubitz
First page: 295
Abstract: The isoelectronic relationship of 1,2-azaborinine (B=N structural motif) and benzene (C=C) is well documented. Upon deprotonation of the former, the anionic 1,2-azaboratabenzene is obtained, which is isosteric with pyridine (C=N) and has a similar capability as an aromatic N-donor. We present the complexation of boron and aluminum precursors with a κ2-N,O-donating 8-hydroxy-BN-naphthalene ligand (H2(BQ), 1). Six chelate complexes with 1:1 and 2:1 stoichiometries were isolated and characterized by X-ray diffraction analysis and NMR spectroscopy. Comparing the isosteric dimethylaluminum complexes of H2(BQ) and an 8-hydroxyquinoline (HQ’, 2) as a reference allowed us to quantify the influence of a formal substitution of carbon by boron on the structure and the electronic properties: While the structural parameters of the ligands were similar, the electropositive boron atom affected the electron density distributions within the complexes substantially. As the consequence, the Al–N bond was significantly shortened, and the aluminum atom showed a different coordination geometry than in the quinoline analog. Moreover, strong hypsochromic shifts of both the absorption and the emission were observed. The results highlight that the differences between CN and BN polyaromatic complexes are more distinct than between equally charged BN and CC congeners.
Citation: Inorganics
PubDate: 2023-07-12
DOI: 10.3390/inorganics11070295
Issue No: Vol. 11, No. 7 (2023)
- Inorganics, Vol. 11, Pages 296: In Situ Techniques for Characterization of
Layered Double Hydroxide-Based Oxygen Evolution Catalysts
Authors: Andraž Mavrič, Matjaž Valant
First page: 296
Abstract: Functional layered double hydroxide (LDH) usually contains different cationic substitutes to increase the activity of the oxygen evolution reaction (OER). The intrinsic OER activity of LDH materials is connected with the chemical composition and dispersion of metal cations substitutions in the matrix phase. The potential induced phase transitions, in particular hydroxide-to-oxyhydroxide transitions, are a predisposition for the high OER activity of LDH materials and can be followed by coupling the electrochemical experiments with spectroscopic techniques. The understanding of LDH catalysts under electrochemical conditions also allows an understanding of the behavior of OER catalysts based on transition metals, metal-chalcogenides, -pnictides, -carbides, and metal–organic frameworks. The surfaces of those materials are intrinsically poor OER catalysts. However, they act as precursors to catalysts, which are oxidized into a metal (oxy)hydroxide. This review summarizes the use of in situ techniques for the characterization of LDH-based OER electrocatalysts and presents the influence of these techniques on the understanding of potential induced phase transitions, identification of active sites, and reaction mechanisms.
Citation: Inorganics
PubDate: 2023-07-13
DOI: 10.3390/inorganics11070296
Issue No: Vol. 11, No. 7 (2023)
- Inorganics, Vol. 11, Pages 297: Hierarchical ZSM-5 Zeolite Synthesized
Only with Simple Organic Templates
Authors: Ying Zhao, Yuanchen Li, Peng Cheng, Hongdan Zhang
First page: 297
Abstract: Hierarchical zeolites have attracted more and more attention due to their excellent diffusion and mass transfer performance. However, synthesis of most hierarchical zeolites requires long-chain organic templates, which could increase preparation cost. Here, hierarchical ZSM-5 zeolites were successfully prepared with simple organic templates (triethylenetetramine) in a rotating oven. Besides hierarchical structure, the crystal size of ZSM-5 also decreased when they were synthesized under dynamic hydrothermal conditions. The samples were analyzed using various physicochemical characterizations, such as X-ray diffraction (XRD), X-ray fluorescence (XRF), scanning electron microscopy (SEM), Fourier transform infrared spectra (FT-IR), temperature-programmed desorption of ammonia (NH3-TPD) and N2 adsorption–desorption. The hierarchical ZSM-5 zeolites synthesized in a rotating oven presented better catalytic activity and stability in iso-butane cracking reaction than those synthesized under conventional static hydrothermal conditions.
Citation: Inorganics
PubDate: 2023-07-14
DOI: 10.3390/inorganics11070297
Issue No: Vol. 11, No. 7 (2023)
- Inorganics, Vol. 11, Pages 298: The Mechanical Properties of Geopolymers
from Different Raw Materials and the Effect of Recycled Gypsum
Authors: Henna Korhonen, Juha Timonen, Sari Suvanto, Pipsa Hirva, Kirsi Mononen, Sirpa Jääskeläinen
First page: 298
Abstract: Geopolymers are amorphous inorganic polymers that are mainly used in the construction industry as an environmentally friendly alternative to ordinary cement. This study compared selected mechanical properties (setting time, shrinkage, strength) of geopolymer specimens made from different main raw materials, mainly at room temperature, and investigated the effects of recycled gypsum on these. A structural analysis of the specimens was conducted with XRD and SEM. Also, the leaching of aluminium, silicon, and calcium from the specimens was investigated. According to this study, raw materials have a significant impact on the properties of geopolymers. Recycled gypsum affected the setting time of the geopolymers, but the effect was not the same for all specimens. It increased the setting time of specimens made from calcium-rich raw materials, for example, and the ground-granulated blast furnace slag specimens hardened as fast as ordinary Portland cement (about 300 min), but the addition of gypsum decreased it to 1300 min. Gypsum-containing specimens, based on Ca-deficient metakaolin or fly ash, hardened even faster than OPC, in 100–150 min. Recycled gypsum significantly reduced the plastic shrinkage of most of the 28 d specimens to lower values than those achieved for OPC (0.07%). The only exceptions were the fly-ash-based specimens. However, gypsum had no effect on the drying shrinkage, which accounted for a larger proportion of the total shrinkage in most specimens. Therefore, it had no significant effect on the total shrinkage of the geopolymer specimens. The reducing effect of gypsum on the plastic shrinkage of geopolymers was attributed to ettringite, which was observed in all gypsum-containing specimens analysed with XRD. In this study, recycled gypsum decreased the compressive strength of the specimens, which could be prevented by using a finer gypsum powder.
Citation: Inorganics
PubDate: 2023-07-14
DOI: 10.3390/inorganics11070298
Issue No: Vol. 11, No. 7 (2023)
- Inorganics, Vol. 11, Pages 299: Processing, Phase Stability, and
Conductivity of Multication-Doped Ceria
Authors: Elizabeth Gager, Juan C. Nino
First page: 299
Abstract: Multicomponent doping of ceria with four cations is used as a preliminary investigation into the ionic conductivity of high-entropy-doped ceria systems. Different compositions of Ce1-x(Ndx/4Prx/4Smx/4Gdx/4)O2-δ (x = 0.05, 0.10, 0.15, and 0.20) are synthesized using the oxalate co-precipitation method yielding single-phase oxalate precursors. X-ray diffraction, Raman spectroscopy, and Fourier-transform infrared spectroscopy are used to characterize the precipitated oxalates. Simultaneous thermal gravimetric analysis and differential scanning calorimetry reveal a two-step decomposition of the oxalates into the doped oxide. The ionic conductivity of the samples is measured from 250 °C to 600 °C using electrochemical impedance spectroscopy. All samples exhibit similar grain conductivity values at 600 °C, comparable to singly doped samples. However, an increase in total conductivity is observed with an increase in doping concentration up to 15% followed by a decrease beyond this concentration. These findings suggest that multicomponent doping may not significantly enhance the grain conductivity of doped ceria beyond conventional single and co-doped compositions but can modulate the grain boundary conductivity and thus the total conductivity of ceria ceramics.
Citation: Inorganics
PubDate: 2023-07-14
DOI: 10.3390/inorganics11070299
Issue No: Vol. 11, No. 7 (2023)
- Inorganics, Vol. 11, Pages 300: FeNi Confined in N-Doped Carbon as a
Highly Efficient Bi-Functional Catalyst for Rechargeable Zn–Air
Batteries
Authors: Lei Duan, Zhili Ren, Xiaoling Chen, Ding Zhang, Shoudong Xu
First page: 300
Abstract: Rechargeable zinc–air batteries (RZABs) are basically dependent on both affordable and long-lasting bifunctional electrocatalysts. A non-precious metal catalyst, a FeNi nanoalloy catalyst (FeNi@NC) with an extremely low metal consumption (0.06 mmol), has been successfully synthesized. It shows a high half-wave potential of 0.845 V vs. RHE for ORR and a low overpotential of 318 mV for OER at 10 mA cm−2, favoring a maximum power density of 116 mW cm−2 for the constructed RZABs. The voltage plateau is reserved even after 167 h of cell operation. The synergistic effect between the nano-sized FeNi alloy and nitrogen-doped carbon with abundant N sites mainly contributes to the electrocatalytic activity. This research can provide some useful guidelines for the development of economic and efficient bifunctional catalysts for RZABs.
Citation: Inorganics
PubDate: 2023-07-14
DOI: 10.3390/inorganics11070300
Issue No: Vol. 11, No. 7 (2023)
- Inorganics, Vol. 11, Pages 301: Strain Modulation of Electronic Properties
in Monolayer SnP2S6 and GeP2S6
Authors: Junlei Zhou, Yuzhou Gu, Yue-E Xie, Fen Qiao, Jiaren Yuan, Jingjing He, Sake Wang, Yangsheng Li, Yangbo Zhou
First page: 301
Abstract: In recent years, two-dimensional (2D) materials have attracted significant attention due to their distinctive properties, including exceptional mechanical flexibility and tunable electronic properties. Via the first-principles calculation, we investigate the effect of strain on the electronic properties of monolayer SnP2S6 and GeP2S6. We find that monolayer SnP2S6 is an indirect bandgap semiconductor, while monolayer GeP2S6 is a direct bandgap semiconductor. Notably, under uniform biaxial strains, SnP2S6 undergoes an indirect-to-direct bandgap transition at 4.0% biaxial compressive strains, while GeP2S6 exhibits a direct-to-indirect transition at 2.0% biaxial tensile strain. The changes in the conduction band edge can be attributed to the high-symmetry point Γ being more sensitive to strain than K. Thus, the relocation of the conduction band and valence band edges in monolayer SnP2S6 and GeP2S6 induces a direct-to-indirect and indirect-to-direct bandgap transition, respectively. Consequently, the strain is an effective band engineering scheme which is crucial for the design and development of next-generation nanoelectronic and optoelectronic devices.
Citation: Inorganics
PubDate: 2023-07-15
DOI: 10.3390/inorganics11070301
Issue No: Vol. 11, No. 7 (2023)
- Inorganics, Vol. 11, Pages 302: Homogeneous Metal-Catalyzed Hydrogenation
of CO2 Derivatives: Towards Indirect Conversion of CO2 to Methanol
Authors: Tolganay Andizhanova, Aziza Adilkhanova, Andrey Y. Khalimon
First page: 302
Abstract: The increase in anthropogenic CO2 concentrations and associated environmental issues have demanded the development of technologies for CO2 utilization. Among various potential solutions to decrease CO2 emissions and achieve carbon neutrality, the recycling of post-combustion CO2 into value-added chemicals and fuels is considered one of the most economically attractive processes. In this regard, due to its large global demand and versatile applications in the chemical and energy sectors, methanol serves as the most appealing target for the chemical utilization of CO2. However, direct hydrogenation of CO2 to MeOH has proved challenging due to selectivity issues and high energy input, mainly dependent on CO2-emitting fossil energy sources. To address these challenges, an alternative indirect CO2-to-MeOH methodology has been proposed, which involves the hydrogenation of CO2 via the intermediate formation of well-known CO2 derivatives, such as formates, carbonates, formamides, carbamates, and urea derivatives. Homogeneous transition metal catalysts have been at the center of this research avenue, potentially allowing for more selective and low-temperature alternative routes from CO2 to MeOH. This review aims to highlight the advances and challenges in homogeneous transition metal-catalyzed hydrogenation of major CO2 derivatives to MeOH. Special attention is paid to the mechanisms of such transformations.
Citation: Inorganics
PubDate: 2023-07-15
DOI: 10.3390/inorganics11070302
Issue No: Vol. 11, No. 7 (2023)
- Inorganics, Vol. 11, Pages 303: Dependence of Ge/Si Avalanche Photodiode
Performance on the Thickness and Doping Concentration of the
Multiplication and Absorption Layers
Authors: Hazem Deeb, Kristina Khomyakova, Andrey Kokhanenko, Rahaf Douhan, Kirill Lozovoy
First page: 303
Abstract: In this article, the performance and design considerations of the planar structure of germanium on silicon avalanche photodiodes are presented. The dependences of the breakdown voltage, gain, bandwidth, responsivity, and quantum efficiency on the reverse bias voltage for different doping concentrations and thicknesses of the absorption and multiplication layers of germanium on the silicon avalanche photodiode were simulated and analyzed. The study revealed that the gain of the avalanche photodiode is directly proportional to the thickness of the multiplication layer. However, a thicker multiplication layer was also associated with a higher breakdown voltage. The bandwidth of the device, on the other hand, was inversely proportional to the product of the absorption layer thickness and the carrier transit time. A thinner absorption layer offers a higher bandwidth, but it may compromise responsivity and quantum efficiency. In this study, the dependence of the photodetectors’ operating characteristics on the doping concentration used for the multiplication and absorption layers is revealed for the first time.
Citation: Inorganics
PubDate: 2023-07-15
DOI: 10.3390/inorganics11070303
Issue No: Vol. 11, No. 7 (2023)
- Inorganics, Vol. 11, Pages 304: Transannular Selenocyclofunctionalization
of 1,5-cyclooctadiene: The Antioxidant Properties of
9-selenabicyclo[3.3.1]nonane Derivatives and the Discovery of Increasing
Both GPx and GR Activities
Authors: Maxim V. Musalov, Irina S. Kapustina, Ekaterina V. Spiridonova, Natalya V. Ozolina, Svetlana V. Amosova, Tatyana N. Borodina, Vladimir A. Potapov
First page: 304
Abstract: Oxidative stress is the cause of various pathologies and disorders of cellular functions. Substances that reduce the pathological effect of oxidative stress on homeostasis include organoselenium compounds of natural and synthetic origin. Depending on the structure, organoselenium compounds can exhibit different biological activities, for example, reducing oxidative stress, participating in the regulation of signaling systems, influencing the synthesis of cytokines, etc. This makes them promising products for the development of new means of metabolic correction and drugs with enzyme-like activity. This study is aimed at developing an effective method for the synthesis of functional organoselenium compounds and studying their antioxidant effect in vivo under stress conditions. A one-pot catalyst-free method of transannular addition-functionalization of cis,cis-1,5-cyclooctadiene with selenium dihalides in the presence of nucleophiles was developed. For the first time, the antioxidant activity of functionalized 9-selenabicyclo[3.3.1]nonanes was studied in vivo. Quantitative characteristics of the effect on the level of lipid peroxidation and the activity of glutathione peroxidase and glutathione reductase under stress conditions were obtained. The effect of substituents in the selenium-containing scaffold on the biological activity of the compounds was studied. The water-soluble 9-selenabicyclo[3.3.1]nonane derivatives, containing hydroxyl and 2-hydroxyethoxy groups, which increased the activity of both glutathione peroxidase and glutathione reductase, were discovered.
Citation: Inorganics
PubDate: 2023-07-15
DOI: 10.3390/inorganics11070304
Issue No: Vol. 11, No. 7 (2023)
- Inorganics, Vol. 11, Pages 305: Two Birds with One Stone: Ammonium-Induced
Carbon Nanotube Structure and Low-Crystalline Cobalt Nanoparticles
Enabling High Performance of Lithium-Sulfur Batteries
Authors: Qi Tan, Hongliang Liu, Guozhu Liang, Kaigui Jiang, Hangxuan Xie, Weijie Si, Jiajv Lin, Xiongwu Kang
First page: 305
Abstract: The electrochemical performance of lithium–sulfur batteries (LiSBs) has been hampered by the slow redox kinetics and shuttle effect of lithium polysulfides (LiPSs), which require the rational design and synthesis of highly active electrocatalysts towards this reaction. Herein, worm-like N-doped porous carbon nanotube-supported low-crystalline Co nanoparticles (a-Co-NC@C) were derived from binary Zn–Co ZIF via a two-step thermal annealing method. Initial thermal annealing 950 °C in Ar + H2 atmosphere results in the carbonization of binary Zn–Co ZIF and the formation of high crystalline Co nanoparticles. Thermal annealing in ammonia atmosphere at 350 °C not only results in the reduced crystallinity of cobalt nanoparticles; it also promotes the growth of highly graphitized and heavily N-doped intertwined carbon nanotubes. The enlarged porous carbon nanotube structure offers accommodation for sulfur content, while the doped carbon and Co nanoparticles with reduced crystallinity facilitate the redox kinetics of LiPSs, improving the cycling stability, rate performance and capacity of LiSBs batteries. As a result, the a-Co-NC@C cathode displays a specific capacity of 559 mAh g−1 after 500 cycles at 1 C, and a specific capacity of 572 mAh g−1 at 3 C. It delivers a specific capacity of 579 mAh g−1 at high sulfur loading of a 2.55 mg cm−2 at 1 C after 400 cycles. This work highlights the importance of phase engineering of carbon matrix and transition metal nanoparticles in electrochemical performance of Li-S batteries.
Citation: Inorganics
PubDate: 2023-07-18
DOI: 10.3390/inorganics11070305
Issue No: Vol. 11, No. 7 (2023)
- Inorganics, Vol. 11, Pages 306: How to Address Flame-Retardant Technology
on Cotton Fabrics by Using Functional Inorganic Sol–Gel Precursors
and Nanofillers: Flammability Insights, Research Advances, and
Sustainability Challenges
Authors: Valentina Trovato, Silvia Sfameni, Rim Ben Debabis, Giulia Rando, Giuseppe Rosace, Giulio Malucelli, Maria Rosaria Plutino
First page: 306
Abstract: Over the past decade, inorganic fillers and sol–gel-based flame-retardant technologies for textile treatments have gained increasing research interest as useful alternatives to hazardous chemicals previously employed in textile coating and finishing. This review presents the current state of the art of inorganic flame-retardant technology for cotton fabrics to scientists and researchers. Combustion mechanism and flammability, as well as the thermal behavior of neat cotton samples, are first introduced. The main section is focused on assessing the effect of inorganic and sol–gel-based systems on the final flame-retardant properties of cotton fabrics, emphasizing their fire safety characteristics. When compared to organic flame-retardant solutions, inorganic functional fillers have been shown to be more environmentally friendly and pollution-free since they do not emit compounds that are hazardous to ecosystems and humans when burned. Finally, some perspectives and recent advanced research addressing the potential synergism derived from the use of inorganic flame retardants with other environmentally suitable molecules toward a sustainable flame-retardant technological approach are reviewed.
Citation: Inorganics
PubDate: 2023-07-18
DOI: 10.3390/inorganics11070306
Issue No: Vol. 11, No. 7 (2023)
- Inorganics, Vol. 11, Pages 307: The Tripodal Ligand’s 4f Complexes:
Use in Molecular Magnetism
Authors: Kira E. Vostrikova
First page: 307
Abstract: A predictable type of coordination is a key property of tripodal ligands. Homo- and heteroleptic lanthanide complexes with tripodal ligands are a representative class of compounds. However, despite the fact that many of them are paramagnetic, their magnetic behavior is poorly studied. This is because their photophysical and catalytic properties are considered more attractive. In the present review, we try to summarize the available structural information and only a few examples of data on magnetic properties in order to draw some conclusions about the prospect of such ligands in the design of quantum molecular magnets involving lanthanide (Ln) ions. We would also like to catch the reader’s attention to the fact that, despite the consideration of a large part of the currently known Ln compounds with tripodal ligands, this review is not exhaustive. However, our goal is to draw the attention of magnetochemists and theoreticians to a whole niche of air-stable Ln complexes that is still out of their field of vision.
Citation: Inorganics
PubDate: 2023-07-20
DOI: 10.3390/inorganics11070307
Issue No: Vol. 11, No. 7 (2023)
- Inorganics, Vol. 11, Pages 308: Review on the Chemistry of [M(NH3)n](XO4)m
(M = Transition Metal, X = Mn, Tc or Re, n = 1–6, m = 1–3)
Ammine Complexes
Authors: Raj Narain Mehrotra
First page: 308
Abstract: The preparation of ammine complexes of transition metals having oxidizing anions such as permanganate and perrhenate ions is a great challenge due to possible reactions between ammonia and oxidizing anions during the synthesis of these materials. However, it has an important role in both the development of new oxidants in organic chemistry and especially in the preparation of mixed-metal oxide catalyst precursors and metal alloys for their controlled temperature decomposition reactions. Therefore, in this paper, synthetic procedures to prepare ammonia complexes of transition metal permanganate, pertechnetate, and perrhenate (the VIIB group tetraoxometallates) salts have been comprehensively reviewed. The available data about these compounds’ structures and spectroscopic properties, including the presence of hydrogen bonds that act as redox reaction centers during thermal decomposition, are given and evaluated in detail. The nature of the thermal decomposition products has also been summarized. The available information about the role of the ammine complexes of transition metal permanganate salts in organic oxidation reactions, such as the oxidation of benzyl alcohols and regeneration of oxo-compounds from oximes and phenylhydrazones, including the kinetics of these processes, has also been collected. Their physical and chemical properties, including the thermal decomposition characteristics of known diammine (Ag(I), Cd, Zn, Cu(II), Ni(II)), triammine (Ag(I)), and simple or mixed ligand tetraammine (Cu(II), Zn, Cd, Ni(II), Co(II), Pt(II), Pd(II), Co(III)), Ru(III), pentaammine (Co(III), Cr(III), Rh(III) and Ir(III)), and hexaammine (Ni(II), Co(III), Cr(III)) complexes of transition metals with tetraoxometallate(VII) anions (M = Mn, Tc and Re), have been summarized. The preparation and properties of some special mixed ligand/anion/cation-containing complexes, such as [Ru(NH3)4(NO)(H2O)](ReO4)2, [Co(NH3)5(H2O)](ReO4)2, [Co(NH3)5X](MnO4)2 (X = Cl, Br), [Co(NH3)6]Cl2(MnO4), [Co(NH3)5ReO4]X2 (X = Cl, NO3, ClO4, ReO4), and K[Co(NH3)6]Cl2(MnO4)2, are also included.
Citation: Inorganics
PubDate: 2023-07-20
DOI: 10.3390/inorganics11070308
Issue No: Vol. 11, No. 7 (2023)
- Inorganics, Vol. 11, Pages 309: Biologically Synthesized Silver
Nanoparticles Efficiently Control Plant Pathogenic Bacteria-Erwinia
carotovora and Ralstonia solanacearum
Authors: Zainab Bibi, Mohammad Ali, Mohammed Abohashrh, Imtiaz Ahmad, Haji Khan, Murad Ali, Fazal Akbar, Nisar Ahmad, Arshad Iqbal, Farman Ullah, Zahid Ullah, Tahir Muhmood
First page: 309
Abstract: Biogenic nanoparticles are considered effective alternatives to chemical pesticides for the management of pathogenic plant diseases. This study was focused on the synthesis of stable silver nanoparticles (AgNPs) to control challenging plant pathogenic bacteria in vitro and in planta. We synthesized AgNPs by reacting different proportions of silver nitrate and aqueous extract of Hedera nepalensis. The physicochemical properties of the synthesized AgNPs were determined by using various physical techniques. The TEM analysis revealed the AgNPs less than 50 nm in size and spherical shaped. For antibacterial assays, different concentrations (1000–15.62 µg/mL, 2-fold dilutions) of the extract-free AgNPs (Ef-AgNPs) or extract-mixed AgNPs (Em-AgNPs), and fruit extracts (FE) were used against plant pathogenic bacteria Erwinia carotovora subsp. carotovora, Erwinia carotovora subsp. atroseptica, and Ralstonia solanacearum. In the in vitro assays, we found significant inhibition of both bacterial species in response to maximum concentrations of AgNPs. Overall, Ef-AgNPs exhibited a higher percent inhibition of bacterial pathogens. In potato tubers assay, complete inhibition of Erwinia carotovora was observed, except for the lowest AgNPs concentration of 15.62 µg/mL. Similarly, exposure of tomato plants to Ralstonia solanacearum suspensions (OD600 = 0.2) in the soil-drenching experiment and post-exposure treatment with 1000 µg/mL and 125 µg/mL of AgNPs resulted in disease inhibition. This study provides the basis that biogenic nanoparticles prepared from Hedera nepalensis are one of the best substitutes to synthetic pesticide, having displayed better results to control the growth of phytopathogenic microbes. However, field studies need to be conducted in a controlled environment to scale up the current work and find out the efficacy of nanoparticles on a larger scale.
Citation: Inorganics
PubDate: 2023-07-20
DOI: 10.3390/inorganics11070309
Issue No: Vol. 11, No. 7 (2023)
- Inorganics, Vol. 11, Pages 310: Redox Targets for
Phosphine–Boranes
Authors: Yonatan Morocz, Rachel E. Greben, Leonard A. Levin
First page: 310
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 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.
Citation: Inorganics
PubDate: 2023-07-22
DOI: 10.3390/inorganics11070310
Issue No: Vol. 11, No. 7 (2023)
- Inorganics, Vol. 11, Pages 311: MoO3 Solubility and Chemical Durability of
V2O5-Bearing Borosilicate Glass
Authors: Minako Nagata, Toru Sugawara
First page: 311
Abstract: In the vitrification of high-level radioactive liquid waste (HLW), the separation of sodium-molybdate melts is a problem because it reduces the chemical durability of the vitrified waste. A glass with both high MoO3 solubility and chemical durability is required for the safe disposal of radioactive waste. In this study, we investigate the effects of vanadium oxide on the phase separation of the molybdenum-rich phase and the water resistance of the resulting glass by phase equilibrium experiments and chemical durability test. Phase equilibrium experiments were performed on SiO2-B2O3-Al2O3-ZnO-CaO-Na2O-LiO2-MoO3 system glasses and on glasses with V2O5 added. The results showed that MoO3 solubility increased when V2O5 was added. The increase in MoO3 solubility in borosilicate melts may be associated with the viscosity-lowering effect of V2O5. Chemical durability tests were performed on borosilicate glass compositions obtained from phase equilibrium experiments. The normalized leaching rates of V2O5-bearing glasses were higher than those of other glasses. This is due to the higher network modifier/network former ratio of the glass tested. The normalized elemental mass loss of glass containing waste components increases with increasing leaching duration. This suggests that the waste component prevents the formation of a gel layer at the reaction front.
Citation: Inorganics
PubDate: 2023-07-24
DOI: 10.3390/inorganics11070311
Issue No: Vol. 11, No. 7 (2023)
- Inorganics, Vol. 11, Pages 312: Structure–Function Relationship
within Cu-Peptoid Electrocatalysts for Water Oxidation
Authors: Guilin Ruan, Natalia Fridman, Galia Maayan
First page: 312
Abstract: Water oxidation (WO) is the first step in the water-splitting process aiming at the production of hydrogen as a green renewable fuel. To successfully perform WO, potent strategies for overcoming the high energetic barrier and slow kinetics of this reaction are urgently required. One such strategy is the use of molecular catalysis. Specifically, Cu-based catalysts have been highlighted over the last decade due to their stability and fast kinetics. Among them, Cu-peptoids, where peptoids are peptidomimetics akin to peptides and are N-substituted glycine oligomers, can act as stable and active catalysts for oxidation transformations including electrocatalytic WO. Previously, we suggested that a benzyl group incorporated as a side chain near the catalytic site within a Cu-peptoid electrocatalyst for WO has a structural role in the activity of the electrocatalyst in phosphate buffer (PBS). Herein, we aimed to test this hypothesis and understand how an incorporated structural element side chain affects WO. To this aim, we prepared a set of peptoid trimers each with a different structural element replacing the benzyl group by either naphthyl, cyclohexyl, benzyl, propyl chloride, or propyl side chains as well as a peptoid lacking a structural element. We studied the structure of their Cu complexes and tested these complexes as electrocatalysts for WO. We discovered that while all the peptoids self-assemble to form dinuclear Cu-peptoid complexes, the duplex that has no structural side chain, Cu2(BE)2, is structurally different from the others in the solid state. Moreover, Cu2(BE)2 remains dinuclear in a PBS at pH 11, while all the other duplexes are mononuclear in the PBS. Finally, though most of the complexes showed low electrocatalytic activity for WO, the dinuclear complex Cu2(BE)2 performed with the highest turnover frequency of 484 s−1. Nevertheless, this dinuclear complex slowly decomposes to the corresponding mononuclear complex as a more stable species during WO, while the other mononuclear complexes retain their structure in solution but display much slower kinetics (ca. 5 to 8 s−1) under the same conditions. Overall, our results demonstrate that bulkier side chains hamper the stability of dinuclear Cu-peptoids in a PBS, and hence, their efficiency as WO electrocatalysts is also hampered.
Citation: Inorganics
PubDate: 2023-07-24
DOI: 10.3390/inorganics11070312
Issue No: Vol. 11, No. 7 (2023)
- Inorganics, Vol. 11, Pages 313: Pr@C82 Metallofullerene: Calculated
Isomeric Populations
Authors: Zdeněk Slanina, Filip Uhlík, Takeshi Akasaka, Xing Lu, Ludwik Adamowicz
First page: 313
Abstract: Relative equilibrium populations of the five lowest-energy isolated-pentagon-rule (IPR) isomeric structures of Pr@C82 under high-temperature fullerene synthesis conditions were calculated with the Gibbs energy terms based on molecular characteristics derived using density functional theory (DFT) treatments (B3LYP/6-31+G*∼SDD energetics and B3LYP/6-31G*∼SDD entropy). Two leading isomers were identified, major Pr@C2v;9-C82 and minor Pr@Cs;6-C82. The calculated isomeric relative equilibrium populations agreed with observations.
Citation: Inorganics
PubDate: 2023-07-24
DOI: 10.3390/inorganics11070313
Issue No: Vol. 11, No. 7 (2023)
- Inorganics, Vol. 11, Pages 375: Probing the Bioinorganic Chemistry of
Cu(I) with 111Ag Perturbed Angular Correlation (PAC) Spectroscopy
Authors: Victoria Karner, Attila Jancso, Lars Hemmingsen
First page: 375
Abstract: The two most common oxidation states of copper in biochemistry are Cu(II) and Cu(I), and while Cu(II) lends itself to spectroscopic interrogation, Cu(I) is silent in most techniques. Ag(I) and Cu(I) are both closed-shell d10 monovalent ions, and to some extent share ligand and coordination geometry preferences. Therefore, Ag(I) may be applied to explore Cu(I) binding sites in biomolecules. Here, we review applications of 111Ag perturbed angular correlation (PAC) of γ-ray spectroscopy aimed to elucidate the chemistry of Cu(I) in biological systems. Examples span from small blue copper proteins such as plastocyanin and azurin (electron transport) over hemocyanin (oxygen transport) to CueR and BxmR (metal-ion-sensing proteins). Finally, possible future applications are discussed. 111Ag is a radionuclide which undergoes β-decay to 111Cd, and it is a γ-γ cascade of the 111Cd daughter nucleus, which is used in PAC measurements. 111Ag PAC spectroscopy may provide information on the coordination environment of Ag(I) and on the structural relaxation occurring upon the essentially instantaneous change from Ag(I) to Cd(II).
Citation: Inorganics
PubDate: 2023-09-23
DOI: 10.3390/inorganics11100375
Issue No: Vol. 11, No. 10 (2023)
- Inorganics, Vol. 11, Pages 376: Recent Advances in Lanthanide
Metal–Organic Framework Thin Films Based on Eu, Tb, Gd: Preparation
and Application as Luminescent Sensors and Light-Emitting Devices
Authors: Helena Brunckova, Erika Mudra, Ivan Shepa
First page: 376
Abstract: Lanthanide Metal–Organic Frameworks (LnMOFs), in recent years, have developed into an interesting subclass of MOFs. While the number of published papers, in particular, were dedicated to their synthesis and functional properties, along with the application mechanisms of MOFs, only a few of them have been focused on LnMOFs thin films independently. LnMOFs have become interesting thanks to their outstanding properties, for example, excellent structural flexibility, tunable pore size, surface area, functionality, and good chemical stability. Significant progress over the past two decades in the preparation of MOF films has been achieved, especially towards the development of green, or at least greener, synthesis approaches. We begin with insight into various types of MOFs and summarize recent achievements in the production of LnMOF films, along with various film preparation approaches. Afterward, we briefly discuss the applications of luminescence features of lanthanide ions in films and their potential as white-light source materials. We also covered films based on Eu, Tb, and Gd with particular accents on different design approaches. Moreover, specifically, luminescent features applied for sensing temperature, a variety of ions, gases, and biomolecules are highlighted. The review ends with a comprehensive conclusion about the state-of-art-potential of LnMOFs together with an outlook on the future of LnMOF films in future technologies.
Citation: Inorganics
PubDate: 2023-09-23
DOI: 10.3390/inorganics11100376
Issue No: Vol. 11, No. 10 (2023)
- Inorganics, Vol. 11, Pages 377: Mono-Alkyl-Substituted Phosphinoboranes
(HRP–BH2–NMe3) as Precursors for Poly(alkylphosphinoborane)s:
Improved Synthesis and Comparative Study
Authors: Felix Lehnfeld, Tim Oswald, Rüdiger Beckhaus, Manfred Scheer
First page: 377
Abstract: A new synthetic pathway to various mono-alkyl-substituted phosphinoboranes HRP–BH2–NMe3 has been developed. The new synthetic route starting from alkyl halides and NaPH2 followed by metalation and salt metathesis is performed in a one-pot procedure and leads to higher yields and purity of the resulting phosphinoboranes, as compared to previously reported routes. Additionally, the scope of accessible compounds could be expanded from short-chained linear alkyl substituents to longer-chained linear alkyl substituents as well as secondary or functionalized alkyl substituents. The reported examples include primary alkyl-substituted phosphinoboranes RHP-BH2-NMe3 (R = n-butyl, n-pentyl, n-hexyl; 1a–c), the secondary alkyl-substituted derivatives iPrPH-BH2-NMe3 (2), and the functionalized alkyl-substituted 4-bromo-butyl-phosphinoborane (BrC4H8)PH-BH2-NMe3 (3). Compounds 1a, 1c, and 2 were additionally used for preliminary polymerization reactions via a thermal and a transition metal-catalyzed pathway, revealing the formation of high-molecular-weight polymers under certain conditions. Detailed investigations on the influence of temperature, concentration, substituents and reaction time on the respective polymerization reactions were performed.
Citation: Inorganics
PubDate: 2023-09-23
DOI: 10.3390/inorganics11100377
Issue No: Vol. 11, No. 10 (2023)
- Inorganics, Vol. 11, Pages 378: A Computational Perspective on
Carbon-Carbon Bond Formation by Single Cu Atom on Pd(111) Surface for CO
Electrochemical Reduction
Authors: Chen-Cheng Liao, Tsung-Han Tsai, Chun-Chih Chang, Ming-Kang Tsai
First page: 378
Abstract: This study focuses on the computational characterization of electrochemical C-C bond formation through the CO and CHO coupling process utilizing a dioxo-coordinated Cu single atom site ([CuO2]*) supported on a Pd(111) surface. The stable intermediate, [CuO2]*(CO)2, was identified as a tetradentate-and-tetrahedral species formed upon exposure to CO gaseous molecules. Electrochemically, the hydrogenation of the carbonyl group to CHO was found to be 0.87 eV, conceivably lower than the corresponding step for conventional Cu surfaces. This study observed a considerable charge transfer effect from the top layer of Pd atoms to the adsorbate moiety, especially at the TS structure. This phenomenon resulted in an accessible C-C bond formation barrier at 0.67 eV. Furthermore, the reaction energy of C-C bond formation was found to be exothermic at −0.21 eV, indicating a favorable chemical equilibrium condition. Considering the temperature effect and pressure of the gaseous molecules (CO, CO2, O2), the [CuO2]*(CO)2 intermediate was substantially populated at room temperature and was found to be chemically resilient under dry ambient conditions, as suggested by the kinetic modeling results.
Citation: Inorganics
PubDate: 2023-09-24
DOI: 10.3390/inorganics11100378
Issue No: Vol. 11, No. 10 (2023)
- Inorganics, Vol. 11, Pages 379: Synthesis of a New Dinuclear Cu(I) Complex
with a Triazine Ligand and Diphenylphosphine Methane: X-ray Structure,
Optical Properties, DFT Calculations, and Application in DSSCs
Authors: Carlos A. Peñuelas, José J. Campos-Gaxiola, Rody Soto-Rojo, Adriana Cruz-Enríquez, Edgar A. Reynoso-Soto, Valentín Miranda-Soto, Juventino J. García, Marcos Flores-Álamo, Jesús Baldenebro-López, Daniel Glossman-Mitnik
First page: 379
Abstract: A new copper(I) complex, [Cu2(L)2dppm](PF6)2 (1) [L = 3-(2-Pyridyl)-5,6-diphenyl-1,2,4-triazine and dppm: Bis(diphenylphosphino)methane], was prepared and characterized by IR, 1H-NMR, 31P-NMR spectroscopy, elemental and thermogravimetric analysis, and a single-crystal X-ray diffraction technique. Complex 1 is a dinuclear compound, showing that L and dppm act as tridentate and bidentate chelating ligands, respectively. The two Cu(I) atoms exhibit a distorted tetrahedral coordination sphere embedded in N3P environments. The supramolecular interactions in the solid-state structure are characterized by C−H···N, C−H···F, C-H···π and π···π intermolecular interactions, which we studied using Hirshfeld surface and fingerprint tools. Additionally, the complex was studied experimentally using UV–Vis spectroscopy and cyclic voltammetry, and theoretical studies with time-dependent density functional theory (TD-DFT) were performed. Moreover, the optical and electrochemical properties were studied, focusing on the band gap. Compound 1 was used as a co-sensitizer in a dye-sensitized solar cell, showing a good photovoltaic performance of 2.03% (Jsc = 5.095 mAcm−2, Voc = 757 mV, and FF = 52.7%) under 100 mW cm−2 (AM 1.5G) solar irradiation, which is similar to that of DSSC, which was only sensitized by N719 (2.2%) under the same condition.
Citation: Inorganics
PubDate: 2023-09-25
DOI: 10.3390/inorganics11100379
Issue No: Vol. 11, No. 10 (2023)
- Inorganics, Vol. 11, Pages 380: Photooxidative Dehydrogenation of Chiral
Ir (III) Amino Acid Complexes Based on [Λ-Ir(ppy)2(MeCN)2](PF6)
Authors: Suyang Yao, Yanxi Pu, Lulu Ren, Manli Cao, Baohui Ye
First page: 380
Abstract: Octahedral chiral-at-metal Ir(III) complexes exhibit excellent structural stability and stereoselectivity in asymmetric synthesis. Selectively oxidative dehydrogenation of amino acids could be achieved by exploiting such complexes as chiral templates. The obtaining stable imine complexes can then be utilized in nucleophilic additions to generate corresponding chiral amine compounds. In this study, a conveniently synthesized [Λ-Ir(ppy)2(MeCN)2](PF6) chiral complex (ppy is 2-phenylpyridine) was utilized as a chiral template. A series of chiral amino acid complexes Λ-[Ir(ppy)2(D/L-AA)] (AA is amino acid) were prepared in high yield and optical purity. The above amino acid complexes were then oxidized to their corresponding imino acid complexes Λ-[Ir(ppy)2(AA-2H)] under visible light. All these complexes exhibited high selectivity during the dehydrogenation process without the formation of C-N bond coupling byproducts. The photooxidative dehydrogenation rates of these complexes were studied, which show that D-configured amino acids exhibited faster dehydrogenation rates when using the Λ-configured complex as a chiral template and the substitution of electron-donating or bulky groups in the N-α position of the amino acid decreased their dehydrogenation rates. The crystal structures of Λ-Ir(ppy)2(D-Thr) (Thr is threonine) and its dehydrogenated complex Λ-Ir(ppy)2(Thr-2H) indicate the process of photooxidative dehydrogenation and the configuration stability of metal center throughout the process.
Citation: Inorganics
PubDate: 2023-09-25
DOI: 10.3390/inorganics11100380
Issue No: Vol. 11, No. 10 (2023)
- Inorganics, Vol. 11, Pages 381: Formation of Ketimines from Aldimines in
Schiff Base Condensation of Amino Acids and Imidazole-2-Carboxaldehydes:
Tautomerization of Schiff Bases of Amino Acids Resulting in the Loss of
Stereogenic Center
Authors: Greg Brewer, Cynthia Brewer, Raymond J. Butcher, Peter Zavalij
First page: 381
Abstract: The Schiff base reaction of imidazole-2-carboxaldehydes with the anion of alanine, leucine and phenylalanine in the presence of nickel(II) ion gives the neutral NiL2 complexes. The Schiff base ligand, L, binds through an imidazole nitrogen, NIm, the amino acid nitrogen, NAA, and a carboxylate oxygen, O, atom. The two N2O ligands bind to the nickel(II) in a meridional fashion with the NIm and O of each ligand in trans positions. These ligands can exist as the anticipated aldimine, Im − CH = NAA − CH(R) − CO2−, or the ketimine, Im − CH2NAA = C(R) − CO2−, tautomer. Tautomerization of the initially formed aldimine Schiff base results in movement of the hydrogen atom of the alpha carbon of the amino acid to the aldehyde carbon, CAld, atom of the imidazole carboxaldehyde with resultant relocation of the imine double bond in the reverse direction. Ten structures of the structurally unprecedented ketimine tautomer, prepared from imidazole-2-carboxaldehydes and a pyrazole-3-carboxaldehyde, were presented. The structural data supported the formation of the ketimines in each case, while the aldimine tautomer was observed with imidazole-4-carboxaldehydes. A rationale of this can be explained on the basis of charge distribution in the likely intermediate in the tautomerization.
Citation: Inorganics
PubDate: 2023-09-25
DOI: 10.3390/inorganics11100381
Issue No: Vol. 11, No. 10 (2023)
- Inorganics, Vol. 11, Pages 382: Synthesis, Crystal Structure Analyses, and
Antibacterial Evaluation of the Cobalt(II) Complex with
Sulfadiazine-Pyrazole Prodrug
Authors: Mezna Saleh Altowyan, Matti Haukka, Mohammed Salah Ayoup, Magda M. F. Ismail, Nagwan G. El Menofy, Saied M. Soliman, Assem Barakat, Mona M. Sharaf, Morsy A. M. Abu-Youssef, Amal Yousri
First page: 382
Abstract: The complex [Co(L)(H2O)4](NO3)2 of (E)-4-(2-(3-methyl-5-oxo-1-(pyridin-2-yl)-1H-pyrazol-4(5H)-ylidene)hydrazinyl)-N-(pyrimidin-2-yl)benzenesulfonamide (L) was synthesized via the self-assembly technique. Its molecular and supramolecular structures were analyzed using FTIR, elemental analyses, and single-crystal X-ray diffraction, as well as Hirshfeld calculations. This complex crystallized in the triclinic space group P1¯ with Z = 2. The crystallographic asymmetric unit comprised one complex cation and two nitrate counter anions. This complex had distorted octahedral geometry around the Co(II) ion. Numerous intermolecular interactions affecting the molecular packing of this complex were conformed using Hirshfeld investigations. The most significant contacts for the cationic inner sphere [Co(L)(H2O)4]2+ were O···H (38.8%), H···H (27.8%), and N···H (9.9%). On the other hand, the main interactions for the counter NO3¯ ions were the O···H (79.6 and 77.8%), O···N (8.0%), and O···C (9.1%). A high propensity for making interactions for each atom pair in the contacts O…H, N…C, N…H, and C…C was revealed by enrichment ratio values greater than 1. The antibacterial efficacy of the complex and the free ligand were assessed. The free ligand had higher antibacterial activity (MIC = 62.5–125 µg/mL) than the [Co(L)(H2O)4](NO3)2 complex (MIC ≥ 250 µg/mL) versus all the studied bacteria.
Citation: Inorganics
PubDate: 2023-09-25
DOI: 10.3390/inorganics11100382
Issue No: Vol. 11, No. 10 (2023)
- Inorganics, Vol. 11, Pages 383: Dispersion Stability of Carbon Nanotubes
and Their Impact on Energy Storage Devices
Authors: Chunghyeon Choi, Tae Gwang Yun, Byungil Hwang
First page: 383
Abstract: Carbon nanotubes (CNTs), with their extraordinary combination of mechanical, electrical, and thermal properties, have emerged as a revolutionary class of nanomaterials with immense potential in energy storage and harvesting devices. Realizing this potential hinges on a fundamental challenge: the dispersion stability of CNTs within various matrices. This review paper provides a comprehensive exploration of the critical interplay between CNT dispersion stability and its far-reaching implications for the performance of energy storage and harvesting technologies. By delving into the underlying mechanisms of dispersion, the strategies to achieve stability, and the direct effects on device functionality, this review sheds light on the intricate relationship between nanotube dispersion and the advancement of energy-related applications.
Citation: Inorganics
PubDate: 2023-09-25
DOI: 10.3390/inorganics11100383
Issue No: Vol. 11, No. 10 (2023)
- Inorganics, Vol. 11, Pages 384: Revealing the Minimum Energy Pathways for
Formamide Hydrogenation Reactions in the Presence of Platinum and
Platinum–Vanadium Clusters: A Quantum Chemical DFT/Nudged Elastic
Band Study
Authors: Natalia S. Panina, Ilya N. Klyukin, Tatyana M. Buslaeva, Andrei I. Fischer
First page: 384
Abstract: A detailed study on the stages of catalytic reactions involving platinum and platinum-vanadium clusters has been carried out. Minimum energy pathways (MEP) of reactions have been constructed via the DFT/PBE0/def2tzvp method using NEB functional and optimized structures, and points of minima and transition states have been calculated. A two-step process for the conversion of formamide to methylamine under the action of H2 has been considered as a test reaction. The energy barriers of this reaction, not previously described in the literature, have been evaluated. It has been shown that the main changes in the structural characteristics of the reagents, as well as the migration of single H atoms from one metal center of clusters to another or to an organic substrate, are initiated at the molecular level by shifts corresponding to the vectors of normal vibrations of systems in transition states.
Citation: Inorganics
PubDate: 2023-09-25
DOI: 10.3390/inorganics11100384
Issue No: Vol. 11, No. 10 (2023)
- Inorganics, Vol. 11, Pages 385: Benzimidazol-2-ylidene Silver Complexes:
Synthesis, Characterization, Antimicrobial and Antibiofilm Activities,
Molecular Docking and Theoretical Investigations
Authors: Uğur Tutar, Cem Çelik, Elvan Üstün, Namık Özdemir, Neslihan Şahin, David Sémeril, Nevin Gürbüz, İsmail Özdemir
First page: 385
Abstract: Five silver(I) complexes, namely chloro[1-methallyl-3-benzyl)benzimidazol-2-ylidene] silver (6), chloro[1-methallyl-3-(2,3,5,6-tetramethylbenzyl)benzimidazol-2-ylidene]silver (7), chloro[1-methallyl-3-(3,4,5-trimethoxylbenzyl)benzimidazol-2-ylidene]silver (8), chloro[1-methallyl- 3-(naphthylmethyl)benzimidazol-2-ylidene]silver (9), and chloro [1-methallyl-3-(anthracen-9-yl- methyl)benzimidazol-2-ylidene]silver (10), were prepared starting from their corresponding benzimidazolium salts and silver oxide in 71–81% yields. A single-crystal X-ray structure of 7 was determined. These five Ag-NHC complexes were evaluated for their antimicrobial and biofilm formation inhibition properties. Complex 10 exhibited high antimicrobial activities comparable to those obtained with standard drugs such as Fluconazole in contact with Staphylococcus aureus, Enterococcus faecalis, Escherichia coli, Acinetobacter baumannii, and Candida albicans. The latter complex has been shown to be very efficient in antibiofilm activity, with 92.9% biofilm inhibition at 1.9 μg/mL on Escherichia coli. Additionally, the molecules were optimized with DFT-based computational methods for obtaining insight into the structure/reactivity relations through the relative energies of the frontier orbitals. The optimized molecules were also analyzed by molecular docking method against DNA gyrase of Escherichia coli and CYP51 from Candida albicans.
Citation: Inorganics
PubDate: 2023-09-27
DOI: 10.3390/inorganics11100385
Issue No: Vol. 11, No. 10 (2023)
- Inorganics, Vol. 11, Pages 386: Diameter-Selective Host-Guest Interactions
between Functionalized Fullerenes and Single-Walled Carbon Nanotubes
Authors: Rui Zhang, Wanru Gao, Chang Sun, Yiwen Liu, Xiaojun Lu, Xing Lu
First page: 386
Abstract: Carbon nano peapods, with their electronic properties and spintronics, have attracted great attention regarding their potential applications when combined with fullerenes or their derivatives encapsulated inside. Herein, we have designed and synthesized a series of fullerene derivatives with different functional groups, which are then encapsulated into single-walled carbon nanotubes (SWCNTs). Accurate morphological characterization with high-resolution TEM reveals a clear correlation between the filling ratio of the peapods and the steric bulk of the functionalized groups. Further spectroscopic characterizations reveal diameter-selective interactions between the fullerene derivatives and SWCNTs, which, in turn, influence the electronic structures of the nanotubes. Our results have shed new light on the controlled synthesis and property-tuning of nano peapods.
Citation: Inorganics
PubDate: 2023-09-27
DOI: 10.3390/inorganics11100386
Issue No: Vol. 11, No. 10 (2023)
