Pub Date : 2023-12-02DOI: 10.3390/inorganics11120470
Panagiota Tryfon, N. Kamou, S. Mourdikoudis, George Vourlias, U. Menkissoglu-Spiroudi, C. Dendrinou-Samara
Nanotechnology presents promising opportunities for enhancing pest management strategies, particularly in protecting active ingredients to prolong their shelf life and effectiveness. Among different approaches, the combination of inorganic nanoparticles with active ingredients such as the main constituents of natural essential oils in one nanoarchitecture is challenging. In this study, hydrophobic calcium hydroxide nanoparticles coated with oleylamime [Ca(OH)2@OAm NPs] were synthesized using microwave-assisted synthesis. These primary NPs were physicochemically characterized and subsequently utilized to prepare nanocapsules (NCs) either alone (Ca NCs) and/or in combination with geraniol at different ratios of Ca(OH)2@OAm NPs and geraniol, i.e. 1:1 (CaGer1 NCs), 1:2 (CaGer2 NCs), and 1:3 (CaGer3 NCs), respectively. Among the formulations, the CaGer2 NCs demonstrated higher encapsulation efficiency (EE) and loading capacity (LC) of 95% and 20%, correspondingly. They exhibited a hydrodynamic size of 306 nm, a ζ-potential of −35 mV, and a monodisperse distribution. Release kinetics of geraniol from CaGer2 NCs indicated a pH-dependent slow release over 96 h at both 25 °C and 35 °C. In vitro antifungal assay against B. cinerea revealed a concentration-dependent activity, and the EC50 values for Ca(OH)2@OAm NPs, Ca NCs, and CaGer2 NCs were estimated to be 654 µg/mL, 395 µg/mL, and 507 µg/mL, respectively. These results underscore the potential of Ca-based nanoformulations to control plant pathogens, suggesting that while Ca NCs showcase potent antifungal attributes, the different architectures/structures play a critical role in the antifungal effectiveness of the nanoformulations that have to be explored further.
{"title":"Microwave-Mediated Synthesis and Characterization of Ca(OH)2 Nanoparticles Destined for Geraniol Encapsulation","authors":"Panagiota Tryfon, N. Kamou, S. Mourdikoudis, George Vourlias, U. Menkissoglu-Spiroudi, C. Dendrinou-Samara","doi":"10.3390/inorganics11120470","DOIUrl":"https://doi.org/10.3390/inorganics11120470","url":null,"abstract":"Nanotechnology presents promising opportunities for enhancing pest management strategies, particularly in protecting active ingredients to prolong their shelf life and effectiveness. Among different approaches, the combination of inorganic nanoparticles with active ingredients such as the main constituents of natural essential oils in one nanoarchitecture is challenging. In this study, hydrophobic calcium hydroxide nanoparticles coated with oleylamime [Ca(OH)2@OAm NPs] were synthesized using microwave-assisted synthesis. These primary NPs were physicochemically characterized and subsequently utilized to prepare nanocapsules (NCs) either alone (Ca NCs) and/or in combination with geraniol at different ratios of Ca(OH)2@OAm NPs and geraniol, i.e. 1:1 (CaGer1 NCs), 1:2 (CaGer2 NCs), and 1:3 (CaGer3 NCs), respectively. Among the formulations, the CaGer2 NCs demonstrated higher encapsulation efficiency (EE) and loading capacity (LC) of 95% and 20%, correspondingly. They exhibited a hydrodynamic size of 306 nm, a ζ-potential of −35 mV, and a monodisperse distribution. Release kinetics of geraniol from CaGer2 NCs indicated a pH-dependent slow release over 96 h at both 25 °C and 35 °C. In vitro antifungal assay against B. cinerea revealed a concentration-dependent activity, and the EC50 values for Ca(OH)2@OAm NPs, Ca NCs, and CaGer2 NCs were estimated to be 654 µg/mL, 395 µg/mL, and 507 µg/mL, respectively. These results underscore the potential of Ca-based nanoformulations to control plant pathogens, suggesting that while Ca NCs showcase potent antifungal attributes, the different architectures/structures play a critical role in the antifungal effectiveness of the nanoformulations that have to be explored further.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":"116 16","pages":""},"PeriodicalIF":2.9,"publicationDate":"2023-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138607530","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-12-01DOI: 10.3390/inorganics11120468
R. Gomila, E. R. Tiekink, A. Frontera
Three homoleptic Hg(S2CNR2)2, for R = ethyl (1), isobutyl (2), and cyclohexyl (3), compounds apparently exhibit a steric-dependent supramolecular association in their crystals. The small group in 1 allows for dimer formation via covalent Hg–S interactions through an eight-membered {–HgSCS}2 ring as the dithiocarbamato ligands bridge centrosymmetrically related Hg atoms; intradimer Hg···S interactions are noted. By contrast, centrosymmetrically related molecules in 2 are aligned to enable intermolecular Hg···S interactions, but the separations greatly exceed the van der Waals radii. The large group in 3 precludes both dimerization and intermolecular Hg···S interactions. Computational chemistry indicates that the potential region at the Hg atom is highly dependent on the coordination geometry about the Hg atom. Intramolecular (1) and intermolecular (2) spodium bonding (SpB) is demonstrated. Even at separations approaching 0.4 Å beyond the sum of the assumed van der Waals radii, the energy of the stabilization afforded by the structure directs SpB in 2 amounts to approximately 2.5 kcal/mol. A natural bond orbital (NBO) analysis points to the importance of the LP(S) → σ*(Hg–S) charge transfer and to the dominance of the dispersion forces and electron correlation to the SpB in 2.
{"title":"A Computational Chemistry Investigation of the Influence of Steric Bulk of Dithiocarbamato-Bound Organic Substituents upon Spodium Bonding in Three Homoleptic Mercury(II) Bis(N,N-dialkyldithiocarbamato) Compounds for Alkyl = Ethyl, Isobutyl, and Cyclohexyl","authors":"R. Gomila, E. R. Tiekink, A. Frontera","doi":"10.3390/inorganics11120468","DOIUrl":"https://doi.org/10.3390/inorganics11120468","url":null,"abstract":"Three homoleptic Hg(S2CNR2)2, for R = ethyl (1), isobutyl (2), and cyclohexyl (3), compounds apparently exhibit a steric-dependent supramolecular association in their crystals. The small group in 1 allows for dimer formation via covalent Hg–S interactions through an eight-membered {–HgSCS}2 ring as the dithiocarbamato ligands bridge centrosymmetrically related Hg atoms; intradimer Hg···S interactions are noted. By contrast, centrosymmetrically related molecules in 2 are aligned to enable intermolecular Hg···S interactions, but the separations greatly exceed the van der Waals radii. The large group in 3 precludes both dimerization and intermolecular Hg···S interactions. Computational chemistry indicates that the potential region at the Hg atom is highly dependent on the coordination geometry about the Hg atom. Intramolecular (1) and intermolecular (2) spodium bonding (SpB) is demonstrated. Even at separations approaching 0.4 Å beyond the sum of the assumed van der Waals radii, the energy of the stabilization afforded by the structure directs SpB in 2 amounts to approximately 2.5 kcal/mol. A natural bond orbital (NBO) analysis points to the importance of the LP(S) → σ*(Hg–S) charge transfer and to the dominance of the dispersion forces and electron correlation to the SpB in 2.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":"4 4","pages":""},"PeriodicalIF":2.9,"publicationDate":"2023-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138627474","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-12-01DOI: 10.3390/inorganics11120465
Katja Engel, Thomas Schleid
The new rubidium-containing erbium sulfide thioarsenate(III) with the structured formula RbEr2S(S2)[AsS2(S2)] was obtained from the syntheses of elemental erbium (Er), arsenic sesquisulfide (As2S3) and rubidium sesquisulfide (Rb2S3) with elemental sulfur (S) at 773 K as transparent, orange, needle-shaped crystals. RbEr2AsS7 crystallizes monoclinically in the space group C2/c with a = 2339.86(12) pm, b = 541.78(3) pm, c = 1686.71(9) pm and β = 93.109(3) ° for Z = 8. The crystal structure features complex [AsS2(S2)]3− anions with two S2− anions and a (S2)2− disulfide dumbbell coordinating end-on as ligands for each As3+ cation. Even outside the ligand sphere of As3+, S2− and (S2)2− can be found as sulfide anions. Two distinct Er3+ cations are surrounded by either nine or seven sulfur atoms. The [ErS9] polyhedra are corner- and face-connected, while the [ErS7] units share common edges, both building chains along [010]. These different chains undergo edge connectivity with each other, resulting in the formation of corrugated layers, which are held together by Rb+ in chains of condensed [RbS9] polyhedra. So, a three-dimensional network is generated, offering empty channels along [010] apt to take up the As3+ lone-pair cations. Wavelength-dispersive X-ray spectroscopy verified a molar Rb:Er:As:S ratio of approximately 1:2:1:7 and diffuse reflectance spectroscopy showed the typical f–f transitions of Er3+, while the optical band gap was found to be 2.42 eV.
{"title":"RbEr2AsS7: A Rubidium-Containing Erbium Sulfide Thioarsenate(III) with (S2)2− Ligands According to RbEr2S(S2)[AsS2(S2)]","authors":"Katja Engel, Thomas Schleid","doi":"10.3390/inorganics11120465","DOIUrl":"https://doi.org/10.3390/inorganics11120465","url":null,"abstract":"The new rubidium-containing erbium sulfide thioarsenate(III) with the structured formula RbEr2S(S2)[AsS2(S2)] was obtained from the syntheses of elemental erbium (Er), arsenic sesquisulfide (As2S3) and rubidium sesquisulfide (Rb2S3) with elemental sulfur (S) at 773 K as transparent, orange, needle-shaped crystals. RbEr2AsS7 crystallizes monoclinically in the space group C2/c with a = 2339.86(12) pm, b = 541.78(3) pm, c = 1686.71(9) pm and β = 93.109(3) ° for Z = 8. The crystal structure features complex [AsS2(S2)]3− anions with two S2− anions and a (S2)2− disulfide dumbbell coordinating end-on as ligands for each As3+ cation. Even outside the ligand sphere of As3+, S2− and (S2)2− can be found as sulfide anions. Two distinct Er3+ cations are surrounded by either nine or seven sulfur atoms. The [ErS9] polyhedra are corner- and face-connected, while the [ErS7] units share common edges, both building chains along [010]. These different chains undergo edge connectivity with each other, resulting in the formation of corrugated layers, which are held together by Rb+ in chains of condensed [RbS9] polyhedra. So, a three-dimensional network is generated, offering empty channels along [010] apt to take up the As3+ lone-pair cations. Wavelength-dispersive X-ray spectroscopy verified a molar Rb:Er:As:S ratio of approximately 1:2:1:7 and diffuse reflectance spectroscopy showed the typical f–f transitions of Er3+, while the optical band gap was found to be 2.42 eV.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":"21 10","pages":""},"PeriodicalIF":2.9,"publicationDate":"2023-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138627254","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-12-01DOI: 10.3390/inorganics11120466
Fahad Abdulaziz, K. Alabbosh, Odeh Abdullah Odeh Alshammari, Wasan Mohammed Bin Tuwalah, Tahani Y. A. Alanazi, Aleksandra Rakić, Miljan Barić, Milica Marković, V. Jevtović, D. Dimić
Semicarbazones and their transition metal complexes have been investigated as biologically active compounds. This study explores the synthesis, X-ray crystallographic structure, and characterization of a novel Co(III) complex cation with a pyridoxal-isothiosemicarbazone (PLITSC) ligand, [Co(PLITSC-2H)(NH3)3]+. The structure of the complex was further elucidated by the elemental analysis and spectroscopic techniques (IR and UV–VIS). Hirshfeld surface analysis was applied for the investigation of intermolecular interactions governing crystal structure. Optimization was performed at the B3LYP/6-31 + G(d,p)(H,C,N,O,S)/LanL2DZ(Co) level of theory without any geometrical constraints. The selected level of theory’s applicability was proven after comparing experimental and theoretical bond lengths and angles. The antibacterial activity of the complex towards E. coli and B. subtilis was determined and qualified as moderate compared to Streptomycin. The formation of free radical species in the presence of the complex was further verified in the fluorescence microscopy measurements. The molecular docking towards neural nitric-oxide synthase in the brain has shown that the complex structure and relative distribution of ligands were responsible for the binding to amino acids in the active pocket.
{"title":"Crystallographic Structure and Quantum-Chemical Analysis of Biologically Active Co(III)-Pyridoxal–Isothiosemicarbazone Complex","authors":"Fahad Abdulaziz, K. Alabbosh, Odeh Abdullah Odeh Alshammari, Wasan Mohammed Bin Tuwalah, Tahani Y. A. Alanazi, Aleksandra Rakić, Miljan Barić, Milica Marković, V. Jevtović, D. Dimić","doi":"10.3390/inorganics11120466","DOIUrl":"https://doi.org/10.3390/inorganics11120466","url":null,"abstract":"Semicarbazones and their transition metal complexes have been investigated as biologically active compounds. This study explores the synthesis, X-ray crystallographic structure, and characterization of a novel Co(III) complex cation with a pyridoxal-isothiosemicarbazone (PLITSC) ligand, [Co(PLITSC-2H)(NH3)3]+. The structure of the complex was further elucidated by the elemental analysis and spectroscopic techniques (IR and UV–VIS). Hirshfeld surface analysis was applied for the investigation of intermolecular interactions governing crystal structure. Optimization was performed at the B3LYP/6-31 + G(d,p)(H,C,N,O,S)/LanL2DZ(Co) level of theory without any geometrical constraints. The selected level of theory’s applicability was proven after comparing experimental and theoretical bond lengths and angles. The antibacterial activity of the complex towards E. coli and B. subtilis was determined and qualified as moderate compared to Streptomycin. The formation of free radical species in the presence of the complex was further verified in the fluorescence microscopy measurements. The molecular docking towards neural nitric-oxide synthase in the brain has shown that the complex structure and relative distribution of ligands were responsible for the binding to amino acids in the active pocket.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":" 18","pages":""},"PeriodicalIF":2.9,"publicationDate":"2023-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138615601","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-12-01DOI: 10.3390/inorganics11120469
Sonia García-Gómez, J. Giménez, I. Casas, Jordi Llorca, Joan De Pablo
The anodic reactivity of UO2 and UO2 doped with Gd2O3 was investigated by electrochemical methods in slightly alkaline conditions in the presence of silicate and calcium. At the end of the experiments, the electrodes were analysed by X-ray photoelectron spectroscopy to determine the oxidation state of the uranium on the surface. The experiments showed that the increase in gadolinia doping level led to a reduction in the reactivity of UO2, this effect being more marked at the highest doping level studied (10 wt.% Gd2O3). This behaviour could be attributed to the formation of dopant-vacancy clusters (GdIII-Ov), which could limit the accommodation of excess O2− into the UO2 lattice. In addition, the presence of Ca2+ and SiO32− decreased the anodic dissolution of UO2. In summary, the Gd2O3 doping in presence of silicate and calcium was found to strongly decrease the oxidative dissolution of UO2, which is a beneficial situation regarding the long-term management of spent nuclear fuel in a repository.
{"title":"Gd2O3 Doped UO2(s) Corrosion in the Presence of Silicate and Calcium under Alkaline Conditions","authors":"Sonia García-Gómez, J. Giménez, I. Casas, Jordi Llorca, Joan De Pablo","doi":"10.3390/inorganics11120469","DOIUrl":"https://doi.org/10.3390/inorganics11120469","url":null,"abstract":"The anodic reactivity of UO2 and UO2 doped with Gd2O3 was investigated by electrochemical methods in slightly alkaline conditions in the presence of silicate and calcium. At the end of the experiments, the electrodes were analysed by X-ray photoelectron spectroscopy to determine the oxidation state of the uranium on the surface. The experiments showed that the increase in gadolinia doping level led to a reduction in the reactivity of UO2, this effect being more marked at the highest doping level studied (10 wt.% Gd2O3). This behaviour could be attributed to the formation of dopant-vacancy clusters (GdIII-Ov), which could limit the accommodation of excess O2− into the UO2 lattice. In addition, the presence of Ca2+ and SiO32− decreased the anodic dissolution of UO2. In summary, the Gd2O3 doping in presence of silicate and calcium was found to strongly decrease the oxidative dissolution of UO2, which is a beneficial situation regarding the long-term management of spent nuclear fuel in a repository.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":" 24","pages":""},"PeriodicalIF":2.9,"publicationDate":"2023-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138612289","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-12-01DOI: 10.3390/inorganics11120467
Dimitrios Glykos, J. Plakatouras, G. Malandrinos
A novel heteroleptic Ag(I) compound, formulated as [AgL(PPh3)]BF4 (1) (where L represents 2,9-bis((E)-4-methoxystyryl)-1,10-phenanthroline and PPh3 stands for triphenylphosphine), was successfully synthesized and thoroughly characterized. The compound’s stability in solution was confirmed through 1D and 2D nuclear magnetic resonance (NMR). The photo-irradiation of the complex in a CDCl3 solution, utilizing a common portable UV lamp emitting at λ = 365 nm, led to the partial transformation of the E,E-geometric isomer to E,Z, ultimately yielding a 1:1.4 molar ratio of isomers. Its molecular structure was determined via X-ray crystallography, while molecular packing was assessed using Hirshfeld calculations. The most notable interactions (51%) within the cationic inner sphere involved H···H bonds. The photophysical characteristics of the complex and L were evaluated both in the solid state and in solution (dichloromethane). Compound 1 is a weak emitter, with photoluminescence quantum yields of 8.6% and 4.3% in solution and the solid state, respectively.
{"title":"Solution-State Studies, X-ray Structure Determination and Luminescence Properties of an Ag(I) Heteroleptic Complex Containing 2,9-Bis(styryl)-1,10-phenanthroline Derivative and Triphenylphosphine","authors":"Dimitrios Glykos, J. Plakatouras, G. Malandrinos","doi":"10.3390/inorganics11120467","DOIUrl":"https://doi.org/10.3390/inorganics11120467","url":null,"abstract":"A novel heteroleptic Ag(I) compound, formulated as [AgL(PPh3)]BF4 (1) (where L represents 2,9-bis((E)-4-methoxystyryl)-1,10-phenanthroline and PPh3 stands for triphenylphosphine), was successfully synthesized and thoroughly characterized. The compound’s stability in solution was confirmed through 1D and 2D nuclear magnetic resonance (NMR). The photo-irradiation of the complex in a CDCl3 solution, utilizing a common portable UV lamp emitting at λ = 365 nm, led to the partial transformation of the E,E-geometric isomer to E,Z, ultimately yielding a 1:1.4 molar ratio of isomers. Its molecular structure was determined via X-ray crystallography, while molecular packing was assessed using Hirshfeld calculations. The most notable interactions (51%) within the cationic inner sphere involved H···H bonds. The photophysical characteristics of the complex and L were evaluated both in the solid state and in solution (dichloromethane). Compound 1 is a weak emitter, with photoluminescence quantum yields of 8.6% and 4.3% in solution and the solid state, respectively.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":" 31","pages":""},"PeriodicalIF":2.9,"publicationDate":"2023-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138617578","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-11-30DOI: 10.3390/inorganics11120464
Wei Jie Tan, Poernomo Gunawan
To mitigate the effect of CO2 on climate change, significant efforts have been made in the past few decades to capture CO2, which can then be further sequestered or converted into value-added compounds, such as methanol and hydrocarbons, by using thermochemical or electrocatalytic processes. However, CO2 capture and conversion have primarily been studied independently, resulting in individual processes that are highly energy-intensive and less economically viable due to high capital and operation costs. To enhance the overall process efficiency, integrating CO2 capture and conversion into a single system offers an opportunity for a more streamlined process that can reduce energy and capital costs. This strategy can be achieved by employing dual function materials (DFMs), which possess the unique capability to simultaneously adsorb and convert CO2. These materials combine basic metal oxides with active metal catalytic sites that enable both sorption and conversion functions. In this review paper, we focus on the recent strategies that utilize mixed metal oxides as DFMs. Their material design and characteristics, reaction mechanisms, as well as performance and limitations will be discussed. We will also address the challenges associated with this integrated system and attempt to provide insights for future research endeavors.
{"title":"Integration of CO2 Capture and Conversion by Employing Metal Oxides as Dual Function Materials: Recent Development and Future Outlook","authors":"Wei Jie Tan, Poernomo Gunawan","doi":"10.3390/inorganics11120464","DOIUrl":"https://doi.org/10.3390/inorganics11120464","url":null,"abstract":"To mitigate the effect of CO2 on climate change, significant efforts have been made in the past few decades to capture CO2, which can then be further sequestered or converted into value-added compounds, such as methanol and hydrocarbons, by using thermochemical or electrocatalytic processes. However, CO2 capture and conversion have primarily been studied independently, resulting in individual processes that are highly energy-intensive and less economically viable due to high capital and operation costs. To enhance the overall process efficiency, integrating CO2 capture and conversion into a single system offers an opportunity for a more streamlined process that can reduce energy and capital costs. This strategy can be achieved by employing dual function materials (DFMs), which possess the unique capability to simultaneously adsorb and convert CO2. These materials combine basic metal oxides with active metal catalytic sites that enable both sorption and conversion functions. In this review paper, we focus on the recent strategies that utilize mixed metal oxides as DFMs. Their material design and characteristics, reaction mechanisms, as well as performance and limitations will be discussed. We will also address the challenges associated with this integrated system and attempt to provide insights for future research endeavors.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":"40 1","pages":""},"PeriodicalIF":2.9,"publicationDate":"2023-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139200458","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-11-29DOI: 10.3390/inorganics11120463
Andrea Mele, F. Arrigoni, L. De Gioia, C. Elléouet, F. Pétillon, P. Schollhammer, Giuseppe Zampella
Two complexes, related to the active site of [FeFe]-hydrogenases, [Fe2(CO)4(κ2-pma)(µ-bdt)] (1) and [Fe2(CO)4(κ2-pma)(µ-pdt)] (2) (bdt = benzene-1,2-dithiolate, pdt = propane-1,2-dithiolate) featuring the diaza chelate ligand trans-N-(2-pyridylmethylene)aniline (pma) were prepared, in order to study the influence of such a redox ligand, potentially non-innocent, on their redox behaviours. Both complexes were synthesized by photolysis in moderate yields, and they were characterized by IR, 1H and 13C{1H} NMR spectroscopies, elemental analyses and X-ray diffraction. Their electrochemical study by cyclic voltammetry, in the presence and in the absence of protons, revealed different behaviours depending on the aliphatic or aromatic nature of the dithiolate bridge. Density functional theory (DFT) calculations showed the role of the pma ligand as an electron reservoir, allowing the rationalization of the proton reduction process of complex 1.
{"title":"Use of the Asymmetrical Chelating N-Donor 2-Imino-Pyridine as a Redox [Fe4S4] Cubane Surrogate at a Di-Iron Site Related to [FeFe]-Hydrogenases","authors":"Andrea Mele, F. Arrigoni, L. De Gioia, C. Elléouet, F. Pétillon, P. Schollhammer, Giuseppe Zampella","doi":"10.3390/inorganics11120463","DOIUrl":"https://doi.org/10.3390/inorganics11120463","url":null,"abstract":"Two complexes, related to the active site of [FeFe]-hydrogenases, [Fe2(CO)4(κ2-pma)(µ-bdt)] (1) and [Fe2(CO)4(κ2-pma)(µ-pdt)] (2) (bdt = benzene-1,2-dithiolate, pdt = propane-1,2-dithiolate) featuring the diaza chelate ligand trans-N-(2-pyridylmethylene)aniline (pma) were prepared, in order to study the influence of such a redox ligand, potentially non-innocent, on their redox behaviours. Both complexes were synthesized by photolysis in moderate yields, and they were characterized by IR, 1H and 13C{1H} NMR spectroscopies, elemental analyses and X-ray diffraction. Their electrochemical study by cyclic voltammetry, in the presence and in the absence of protons, revealed different behaviours depending on the aliphatic or aromatic nature of the dithiolate bridge. Density functional theory (DFT) calculations showed the role of the pma ligand as an electron reservoir, allowing the rationalization of the proton reduction process of complex 1.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":"76 1","pages":""},"PeriodicalIF":2.9,"publicationDate":"2023-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139211621","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-11-28DOI: 10.3390/inorganics11120462
Nadarajan Prathap, Nagarajan Dravid, Srinivasan R. Kaarmukhilnilavan, M. Shivakumar, S. Venkatesan, M. Shaik, Baji Shaik
The leaf extract of Indigofera linnaei Ali, an Indian medicinal plant, was utilized in the synthesis of copper oxide nanoparticles (CuO-NPs). Green chemistry is a safe and cost-effective method for the synthesis of nanoparticles using plant extracts. The synthesis of CuO NPs was confirmed using ultraviolet–visible (UV-visible) spectrum λ-max data with two peaks at 269 and 337 nm. Different functional groups were identified using Fourier-transform infrared spectroscopy (FT-IR). X-ray diffraction (XRD) was used to confirm the crystalline structure of the CuO-nanoparticles. Scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) analyses were performed to examine the surface morphology and elemental composition of the biosynthesized CuO-NPs. Furthermore, the synthesized CuO-NPs exhibited antibacterial activity against Staphylococcus aureus, Pseudomonas aeruginosa, Escherichia coli, and Enterococcus faecalis. Additionally, they exhibited a good insecticidal effect on Culex quinquefasciatus larvae, with low LC50 55.716 µg/mL and LC90 123.657 µg/mL values. The CuO-NPs inhibited human breast cancer cells in a concentration-dependent manner, with an IC50 value of 63.13 µg/mL.
{"title":"Copper Oxide Nanoparticles Synthesized from Indigofera linnaei Ali and This Plant’s Biological Applications","authors":"Nadarajan Prathap, Nagarajan Dravid, Srinivasan R. Kaarmukhilnilavan, M. Shivakumar, S. Venkatesan, M. Shaik, Baji Shaik","doi":"10.3390/inorganics11120462","DOIUrl":"https://doi.org/10.3390/inorganics11120462","url":null,"abstract":"The leaf extract of Indigofera linnaei Ali, an Indian medicinal plant, was utilized in the synthesis of copper oxide nanoparticles (CuO-NPs). Green chemistry is a safe and cost-effective method for the synthesis of nanoparticles using plant extracts. The synthesis of CuO NPs was confirmed using ultraviolet–visible (UV-visible) spectrum λ-max data with two peaks at 269 and 337 nm. Different functional groups were identified using Fourier-transform infrared spectroscopy (FT-IR). X-ray diffraction (XRD) was used to confirm the crystalline structure of the CuO-nanoparticles. Scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) analyses were performed to examine the surface morphology and elemental composition of the biosynthesized CuO-NPs. Furthermore, the synthesized CuO-NPs exhibited antibacterial activity against Staphylococcus aureus, Pseudomonas aeruginosa, Escherichia coli, and Enterococcus faecalis. Additionally, they exhibited a good insecticidal effect on Culex quinquefasciatus larvae, with low LC50 55.716 µg/mL and LC90 123.657 µg/mL values. The CuO-NPs inhibited human breast cancer cells in a concentration-dependent manner, with an IC50 value of 63.13 µg/mL.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":"127 1","pages":""},"PeriodicalIF":2.9,"publicationDate":"2023-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139227045","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-11-27DOI: 10.3390/inorganics11120460
D. Dimić, Thomas Eichhorn, D. Milenkovic, Goran N. Kaluđerović
Ruthenium(II/III)-based compounds have gained significant interest due to the biocompatibility of ruthenium, its similarity to iron, and the possibility for structural diversification through the choice of ligands. In this contribution, two novel ligands, (2-(2-methoxyethoxy)ethyl nicotinate hydrochloride) and (2-[2-(2-methoxyethoxy)ethoxy]ethyl nicotinate hydrochloride) (pyCOO(CH2CH2O)nCH3: L2, n = 2; L3, n = 3), were synthesized and characterized via ESI-HRMS, as well as IR and NMR spectroscopies. Their structures were optimized at the B3LYP/6-311++G(d,p) level of theory, and NMR chemical shifts were predicted, along with the most important intramolecular interactions. Additionally, two neutral complexes of the general formula [RuCl2(η6-p-cym) (L-κN)] (L = L2: 2; L3: 3) and two cationic complexes of the general formula [RuCl(η6-p-cym)(L-κN)2][PF6] (L = L1: 4; L2: 5) were obtained and characterized. The optimization of the structures was performed at the B3LYP/6-31+G(d,p)(H,C,N,O,Cl)/LanL2DZ(Ru) level of theory. Structural features were described, and intramolecular stabilization interactions were outlined.
{"title":"Synthesis, Structural, and Quantum Chemical Analysis of Neutral and Cationic Ruthenium(II) Complexes with Nicotinate-Polyethylene Glycol Ester Ligands","authors":"D. Dimić, Thomas Eichhorn, D. Milenkovic, Goran N. Kaluđerović","doi":"10.3390/inorganics11120460","DOIUrl":"https://doi.org/10.3390/inorganics11120460","url":null,"abstract":"Ruthenium(II/III)-based compounds have gained significant interest due to the biocompatibility of ruthenium, its similarity to iron, and the possibility for structural diversification through the choice of ligands. In this contribution, two novel ligands, (2-(2-methoxyethoxy)ethyl nicotinate hydrochloride) and (2-[2-(2-methoxyethoxy)ethoxy]ethyl nicotinate hydrochloride) (pyCOO(CH2CH2O)nCH3: L2, n = 2; L3, n = 3), were synthesized and characterized via ESI-HRMS, as well as IR and NMR spectroscopies. Their structures were optimized at the B3LYP/6-311++G(d,p) level of theory, and NMR chemical shifts were predicted, along with the most important intramolecular interactions. Additionally, two neutral complexes of the general formula [RuCl2(η6-p-cym) (L-κN)] (L = L2: 2; L3: 3) and two cationic complexes of the general formula [RuCl(η6-p-cym)(L-κN)2][PF6] (L = L1: 4; L2: 5) were obtained and characterized. The optimization of the structures was performed at the B3LYP/6-31+G(d,p)(H,C,N,O,Cl)/LanL2DZ(Ru) level of theory. Structural features were described, and intramolecular stabilization interactions were outlined.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":"121 1","pages":""},"PeriodicalIF":2.9,"publicationDate":"2023-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139229770","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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