Pub Date : 2024-01-26DOI: 10.3390/inorganics12020041
Y. Kataoka, Kozo Sato, Natsumi Yano, Makoto Handa
Two ferrocenecarboxylate (fca)-bridged dirhodium (Rh2) complexes, [Rh2(fca)4] (1) and [Rh2(fca)(piv)3] (2; piv = pivalate), were prepared through the carboxylate-exchange reactions of [Rh2(O2CCH3)4(H2O)2] and [Rh2(piv)4], respectively, with fcaH and characterized by 1H NMR, ESI-TOF-MS, and elemental analyses. Single-crystal X-ray diffraction analyses of [Rh2(fca)4(MeOH)2] (1(MeOH)2) and [Rh2(fca)(piv)3(MeOH)2] (2(MeOH)2), which are recrystallized from MeOH-containing solutions of 1 and 2, revealed that (1) 1(MeOH)2and 2(MeOH)2possess homoleptic and heteroleptic paddlewheel-type dinuclear structures, respectively; (2) both complexes have a single Rh–Rh bond (2.3771(3) Å for 1(MeOH)2, 2.3712(3) Å for 2(MeOH)2); and (3) the cyclopentadienyl rings of the fca ligands in 1(MeOH)2 adopt an eclipsed conformation, whereas those in 2(MeOH)2 are approximately 12–14° rotated from the staggered conformation. Density functional theory (DFT) calculations revealed that (1) the electronic configurations of the Rh2 core in 1(MeOH)2 and 2(MeOH)2are π4σ2δ2π*2δ*2π*2 and π4σ2δ2δ*2π*4, respectively; and (2) the occupied molecular orbitals (MOs) localized on the fca ligands are energetically degenerate and relatively more unstable than those on the Rh2 cores. Absorption features and electrochemical properties of 1 and 2 were investigated in a 9:1 CHCl3-MeOH solution and compared with those of fcaH and [Rh2(piv)4]. Through examining the obtained results in detail using time-dependent DFT (TDDFT) and unrestricted DFT, we found that 1 and 2 exhibit charge transfer excitations between the fca ligands and Rh2 cores, and 1 shows electronic interactions between ferrocene units through the Rh2 core in the electrochemical oxidation process.
{"title":"Ferrocene-Bearing Homoleptic and Heteroleptic Paddlewheel-Type Dirhodium Complexes","authors":"Y. Kataoka, Kozo Sato, Natsumi Yano, Makoto Handa","doi":"10.3390/inorganics12020041","DOIUrl":"https://doi.org/10.3390/inorganics12020041","url":null,"abstract":"Two ferrocenecarboxylate (fca)-bridged dirhodium (Rh2) complexes, [Rh2(fca)4] (1) and [Rh2(fca)(piv)3] (2; piv = pivalate), were prepared through the carboxylate-exchange reactions of [Rh2(O2CCH3)4(H2O)2] and [Rh2(piv)4], respectively, with fcaH and characterized by 1H NMR, ESI-TOF-MS, and elemental analyses. Single-crystal X-ray diffraction analyses of [Rh2(fca)4(MeOH)2] (1(MeOH)2) and [Rh2(fca)(piv)3(MeOH)2] (2(MeOH)2), which are recrystallized from MeOH-containing solutions of 1 and 2, revealed that (1) 1(MeOH)2and 2(MeOH)2possess homoleptic and heteroleptic paddlewheel-type dinuclear structures, respectively; (2) both complexes have a single Rh–Rh bond (2.3771(3) Å for 1(MeOH)2, 2.3712(3) Å for 2(MeOH)2); and (3) the cyclopentadienyl rings of the fca ligands in 1(MeOH)2 adopt an eclipsed conformation, whereas those in 2(MeOH)2 are approximately 12–14° rotated from the staggered conformation. Density functional theory (DFT) calculations revealed that (1) the electronic configurations of the Rh2 core in 1(MeOH)2 and 2(MeOH)2are π4σ2δ2π*2δ*2π*2 and π4σ2δ2δ*2π*4, respectively; and (2) the occupied molecular orbitals (MOs) localized on the fca ligands are energetically degenerate and relatively more unstable than those on the Rh2 cores. Absorption features and electrochemical properties of 1 and 2 were investigated in a 9:1 CHCl3-MeOH solution and compared with those of fcaH and [Rh2(piv)4]. Through examining the obtained results in detail using time-dependent DFT (TDDFT) and unrestricted DFT, we found that 1 and 2 exhibit charge transfer excitations between the fca ligands and Rh2 cores, and 1 shows electronic interactions between ferrocene units through the Rh2 core in the electrochemical oxidation process.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139593285","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 : 2024-01-25DOI: 10.3390/inorganics12020040
Dong Liu, Yuan Shui, Tao Yang
We performed quantum chemical calculations on the geometries, electronic structures, bonding properties, and stability strategy of endohedral metallofullerenes TM@C28 (TM = Sc−, Y−, La−, Ti, Zr, Hf, V+, Nb+, Ta+). Our calculations revealed that there are three different lowest-energy structures with C2v, C3v, and Td symmetries for TM@C28. The HOMO–LUMO gap of all these structures ranges from 1.35 eV to 2.31 eV, in which [V@C28]+ has the lowest HOMO–LUMO gap of 1.35 eV. The molecular orbitals are mainly composed of fullerene cage orbitals and slightly encapsulated metal orbitals. The bonding analysis on the metal–cage interactions reveals they are dominated by the Coulomb term ΔEelstat and the orbital interaction term ΔEorb, in which the orbital interaction term ΔEorb contributes more than the Coulomb term ΔEelstat. The addition of one or two CF3 groups to [V@C28]+ could increase the HOMO–LUMO gap and further increase the stability of [V@C28]+.
{"title":"Geometries, Electronic Structures, Bonding Properties, and Stability Strategy of Endohedral Metallofullerenes TM@C28 (TM = Sc−, Y−, La−, Ti, Zr, Hf, V+, Nb+, Ta+)","authors":"Dong Liu, Yuan Shui, Tao Yang","doi":"10.3390/inorganics12020040","DOIUrl":"https://doi.org/10.3390/inorganics12020040","url":null,"abstract":"We performed quantum chemical calculations on the geometries, electronic structures, bonding properties, and stability strategy of endohedral metallofullerenes TM@C28 (TM = Sc−, Y−, La−, Ti, Zr, Hf, V+, Nb+, Ta+). Our calculations revealed that there are three different lowest-energy structures with C2v, C3v, and Td symmetries for TM@C28. The HOMO–LUMO gap of all these structures ranges from 1.35 eV to 2.31 eV, in which [V@C28]+ has the lowest HOMO–LUMO gap of 1.35 eV. The molecular orbitals are mainly composed of fullerene cage orbitals and slightly encapsulated metal orbitals. The bonding analysis on the metal–cage interactions reveals they are dominated by the Coulomb term ΔEelstat and the orbital interaction term ΔEorb, in which the orbital interaction term ΔEorb contributes more than the Coulomb term ΔEelstat. The addition of one or two CF3 groups to [V@C28]+ could increase the HOMO–LUMO gap and further increase the stability of [V@C28]+.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-01-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139596423","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}
Fullerenes have a unique structure, capable of both encapsulating other molecules and reacting with those on the exterior surface. Fullerene derivatives have also been found to have enormous potential to address the challenges of the renewable energy sector and current environmental issues, such as in the production of n-type materials in bulk heterojunction solar cells, as antimicrobial agents, in photocatalytic water treatment processes, and in sensor technologies. Endohedral metallofullerenes, in particular, can possess unpaired electron spins, driven by the enclosed metal atom or cluster, which yield valuable magnetic properties. These properties have significant potential for applications in molecular magnets, spin probes, quantum computing, and devices such as quantum information processing,, atomic clocks, and molecular magnets. However, the intrinsically low yield of endohedral fullerenes remains a huge obstacle, impeding not only their industrial utilization but also the synthesis and characterization essential for exploring novel applications. The low yield and difficulty in separation of different types of endohedral fullerenes results in the usage of a large amount of solvents and energy, which is detrimental to the environment. In this paper, we analyse the methodologies proposed by various researchers and identify the critical synthesis parameters that play a role in increasing the yields of fullerenes.
富勒烯具有独特的结构，既能封装其他分子，又能与外表面的分子发生反应。人们还发现，富勒烯衍生物在应对可再生能源领域的挑战和解决当前的环境问题方面具有巨大潜力，例如在生产体异质结太阳能电池中的 n 型材料、用作抗菌剂、光催化水处理工艺和传感器技术方面。特别是内面金属富勒烯，在封闭的金属原子或金属簇的驱动下，可以拥有不成对的电子自旋，从而产生宝贵的磁性。这些特性在分子磁体、自旋探针、量子计算以及量子信息处理、原子钟和分子磁体等设备中有着巨大的应用潜力。然而，内面富勒烯固有的低产率仍然是一个巨大的障碍，不仅阻碍了它们的工业应用，也阻碍了探索新应用所必需的合成和表征。由于产量低且难以分离不同类型的内面富勒烯，因此需要使用大量溶剂和能源，对环境造成了破坏。在本文中，我们分析了不同研究人员提出的方法，并确定了在提高富勒烯产量方面发挥作用的关键合成参数。
{"title":"Process Parameter Optimisation for Endohedral Metallofullerene Synthesis via the Arc-Discharge Method","authors":"Sapna Sinha, Karifa Sanfo, Panagiotis Dallas, Sujay Kumar, Kyriakos Porfyrakis","doi":"10.3390/inorganics12020038","DOIUrl":"https://doi.org/10.3390/inorganics12020038","url":null,"abstract":"Fullerenes have a unique structure, capable of both encapsulating other molecules and reacting with those on the exterior surface. Fullerene derivatives have also been found to have enormous potential to address the challenges of the renewable energy sector and current environmental issues, such as in the production of n-type materials in bulk heterojunction solar cells, as antimicrobial agents, in photocatalytic water treatment processes, and in sensor technologies. Endohedral metallofullerenes, in particular, can possess unpaired electron spins, driven by the enclosed metal atom or cluster, which yield valuable magnetic properties. These properties have significant potential for applications in molecular magnets, spin probes, quantum computing, and devices such as quantum information processing,, atomic clocks, and molecular magnets. However, the intrinsically low yield of endohedral fullerenes remains a huge obstacle, impeding not only their industrial utilization but also the synthesis and characterization essential for exploring novel applications. The low yield and difficulty in separation of different types of endohedral fullerenes results in the usage of a large amount of solvents and energy, which is detrimental to the environment. In this paper, we analyse the methodologies proposed by various researchers and identify the critical synthesis parameters that play a role in increasing the yields of fullerenes.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-01-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139597524","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 : 2024-01-25DOI: 10.3390/inorganics12020039
Kun Zhang, Qiwen Huang, Cun Yang, Xinyao Li
To achieve the peak of carbon dioxide emission and carbon neutrality, utilizing it as a renewable carbon unit in organic synthesis presents an effective chemical solution for sustainable development. In this study, we report a theoretical investigation into the reaction mechanism and the regiodivergence of the Ni-catalyzed [2+2+2] cycloaddition of unsymmetric diynes and CO2 by using DFT calculations. The reaction mechanisms can be classified into two types: one is related to the oxidative coupling of the C≡C moiety with CO2, and the other is related to the oxidative coupling of the two C≡C moieties of diyne. In each type, two possible paths were proposed depending upon the positions of the substituents (H and silyl). Our calculation results indicate that the oxidative coupling of the C≡C moiety and CO2 favors the positions of H-substituent, while the oxidative coupling of the two C≡C moieties is beneficial for inserting CO2 at the positions of silyl-substituent. The regiodivergence is controlled by substrate chain-length and ligand in the different reaction mechanisms.
为了实现二氧化碳的峰值排放和碳中和，在有机合成中利用二氧化碳作为可再生碳单元是实现可持续发展的有效化学解决方案。在本研究中，我们利用 DFT 计算对镍催化的不对称二炔与 CO2 的 [2+2+2] 环加成反应机理和区域发散性进行了理论研究。反应机理可分为两类：一类与 C≡C 分子与 CO2 的氧化偶联有关，另一类与二炔的两个 C≡C 分子的氧化偶联有关。在每种类型中，根据取代基（H 和硅基）的位置，提出了两种可能的途径。我们的计算结果表明，C≡C 基团与 CO2 的氧化偶联有利于 H 取代基的位置，而两个 C≡C 基团的氧化偶联有利于在硅基取代基的位置插入 CO2。在不同的反应机理中，区域差异受底物链长和配体的控制。
{"title":"Theoretical Insights into the Regiodivergence in Ni-Catalyzed [2+2+2] Cycloaddition of Unsymmetric Diynes and CO2","authors":"Kun Zhang, Qiwen Huang, Cun Yang, Xinyao Li","doi":"10.3390/inorganics12020039","DOIUrl":"https://doi.org/10.3390/inorganics12020039","url":null,"abstract":"To achieve the peak of carbon dioxide emission and carbon neutrality, utilizing it as a renewable carbon unit in organic synthesis presents an effective chemical solution for sustainable development. In this study, we report a theoretical investigation into the reaction mechanism and the regiodivergence of the Ni-catalyzed [2+2+2] cycloaddition of unsymmetric diynes and CO2 by using DFT calculations. The reaction mechanisms can be classified into two types: one is related to the oxidative coupling of the C≡C moiety with CO2, and the other is related to the oxidative coupling of the two C≡C moieties of diyne. In each type, two possible paths were proposed depending upon the positions of the substituents (H and silyl). Our calculation results indicate that the oxidative coupling of the C≡C moiety and CO2 favors the positions of H-substituent, while the oxidative coupling of the two C≡C moieties is beneficial for inserting CO2 at the positions of silyl-substituent. The regiodivergence is controlled by substrate chain-length and ligand in the different reaction mechanisms.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-01-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139597659","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 : 2024-01-24DOI: 10.3390/inorganics12020036
Unarine Rambau, Nndivhaleni Anox Masevhe, A. Samie
Green synthesis using plant extracts has emerged as an eco-friendly, clean, and viable alternative to chemical and physical approaches. Herein, the leaf, stem, and root extracts of Lannea discolor were utilized as a reducing and stabilizing agent in synthesizing gold (AuNPs) and copper (CuNPs) nanoparticles. The formation of AuNPs and CuNPs, confirmed by their color change, was characterized by UV-Vis spectroscopy (UV-Vis), scanning electron microscopy analysis, and energy-dispersive X-ray (SEM-EDX), transmission electron microscopy (TEM), and Fourier-transform infrared spectroscopy (FTIR), coupled with minimum inhibitory concentration (MIC) antibacterial assays. Gold nanoflowers (AuNFs), NPs, and CuNPs peaked at wavelengths of 316, 544, and 564 nm, respectively. TEM showed unexpected nanoflowers (30–97 nm) in the leaf extracts and spherical NPs (10–33 nm; 9.3–37.5) from stem and root extracts, while spherical CuNPs (20–104 nm) were observed from all the extracts. EDX confirmed the presence of metal salts, and FTIR revealed stable capping agents. AuNPs and NFs from L. discolor extracts showed appreciable antibacterial activity against Staphylococcus aureus (ATCC 25923), Escherichia coli (ATCC 25922), Pseudomonas aeruginosa (ATCC 27853), Klebsiella pneumoniae (ATCC 700603), and Bacillus subtilis (ATCC 6633) when compared to the plant extracts. At the same time, none was observed from the CuNPs. These AuNPs and CuNPs are particularly appealing in various biomedical and conductivity manufacturing applications due to their shapes and sizes and economical and environmentally friendly production. To our knowledge, this is the first study of the synthesis of gold and copper nanoparticles from L. discolor.
{"title":"Green Synthesis of Gold and Copper Nanoparticles by Lannea discolor: Characterization and Antibacterial Activity","authors":"Unarine Rambau, Nndivhaleni Anox Masevhe, A. Samie","doi":"10.3390/inorganics12020036","DOIUrl":"https://doi.org/10.3390/inorganics12020036","url":null,"abstract":"Green synthesis using plant extracts has emerged as an eco-friendly, clean, and viable alternative to chemical and physical approaches. Herein, the leaf, stem, and root extracts of Lannea discolor were utilized as a reducing and stabilizing agent in synthesizing gold (AuNPs) and copper (CuNPs) nanoparticles. The formation of AuNPs and CuNPs, confirmed by their color change, was characterized by UV-Vis spectroscopy (UV-Vis), scanning electron microscopy analysis, and energy-dispersive X-ray (SEM-EDX), transmission electron microscopy (TEM), and Fourier-transform infrared spectroscopy (FTIR), coupled with minimum inhibitory concentration (MIC) antibacterial assays. Gold nanoflowers (AuNFs), NPs, and CuNPs peaked at wavelengths of 316, 544, and 564 nm, respectively. TEM showed unexpected nanoflowers (30–97 nm) in the leaf extracts and spherical NPs (10–33 nm; 9.3–37.5) from stem and root extracts, while spherical CuNPs (20–104 nm) were observed from all the extracts. EDX confirmed the presence of metal salts, and FTIR revealed stable capping agents. AuNPs and NFs from L. discolor extracts showed appreciable antibacterial activity against Staphylococcus aureus (ATCC 25923), Escherichia coli (ATCC 25922), Pseudomonas aeruginosa (ATCC 27853), Klebsiella pneumoniae (ATCC 700603), and Bacillus subtilis (ATCC 6633) when compared to the plant extracts. At the same time, none was observed from the CuNPs. These AuNPs and CuNPs are particularly appealing in various biomedical and conductivity manufacturing applications due to their shapes and sizes and economical and environmentally friendly production. To our knowledge, this is the first study of the synthesis of gold and copper nanoparticles from L. discolor.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139601703","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 : 2024-01-24DOI: 10.3390/inorganics12020037
Hailong Fei, Peng Wu, Liqing He, Haiwen Li
Micro-nanostructured electrode materials are characterized by excellent performance in various secondary batteries. In this study, a facile and green hydrothermal method was developed to prepare amorphous vanadium-based microspheres on a large scale. Hollow V2O5 microspheres were achieved, with controllable size, after the calcination of amorphous vanadium-based microspheres and were used as cathode materials for lithium-ion batteries. As the quantity of V2O5 microspheres increased, the electrode performance improved, which was ascribed to the smaller charge transfer impedance. The discharge capacity of hollow V2O5 microspheres could be up to 196.4 mAhg−1 at a current density of 50 mAg−1 between 2.0 and 3.5 V voltage limits. This sheds light on the synthesis and application of spherical electrode materials for energy storage.
{"title":"Facile Synthesis of Hollow V2O5 Microspheres for Lithium-Ion Batteries with Improved Performance","authors":"Hailong Fei, Peng Wu, Liqing He, Haiwen Li","doi":"10.3390/inorganics12020037","DOIUrl":"https://doi.org/10.3390/inorganics12020037","url":null,"abstract":"Micro-nanostructured electrode materials are characterized by excellent performance in various secondary batteries. In this study, a facile and green hydrothermal method was developed to prepare amorphous vanadium-based microspheres on a large scale. Hollow V2O5 microspheres were achieved, with controllable size, after the calcination of amorphous vanadium-based microspheres and were used as cathode materials for lithium-ion batteries. As the quantity of V2O5 microspheres increased, the electrode performance improved, which was ascribed to the smaller charge transfer impedance. The discharge capacity of hollow V2O5 microspheres could be up to 196.4 mAhg−1 at a current density of 50 mAg−1 between 2.0 and 3.5 V voltage limits. This sheds light on the synthesis and application of spherical electrode materials for energy storage.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139600355","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 : 2024-01-22DOI: 10.3390/inorganics12010035
S. Armaković, Maria M. Savanović, Mirjana V. Šiljegović, Milica Kisić, Maja Šćepanović, M. Grujić-Brojčin, Nataša Simić, Lazar Gavanski, S. Armaković
The study comprehensively investigates the design and performance of self-cleaning surfaces fabricated by coating aluminum foil with an acrylic paint matrix enriched with different content of titanium dioxide (TiO2) nanoparticles. The main goal was to assess the self-cleaning characteristics of the surfaces obtained. This study employs scanning electron microscopy (SEM) to analyze the morphology of TiO2-modified acrylic surfaces, revealing spherical particles. Raman spectroscopy elucidates signatures characterizing TiO2 incorporation within the acrylic matrix, providing comprehensive insights into structural and compositional changes for advanced surface engineering. Alternating current (AC) impedance spectroscopy was used to assess selected charge transport properties of produced self-cleaning surfaces, allowing us to gain valuable insights into the material’s conductivity and its potential impact on photocatalytic performance. The self-cleaning properties of these tiles were tested against three frequently used textile dyes, which are considered to pose a serious environmental threat. Subsequently, improving self-cleaning properties was achieved by plasma treatment, utilizing a continuous plasma arc. The plasma treatment led to enhanced charge separation and surface reactivity, crucial factors in the self-cleaning mechanism. To deepen our comprehension of the reactive properties of dye molecules and their degradation dynamics, we employed a combination of density functional tight binding (DFTB) and density functional theory (DFT) calculations. This investigation lays the foundation for advancing self-cleaning materials with extensive applications, from architectural coatings to environmental remediation technologies.
{"title":"Self-Cleaning and Charge Transport Properties of Foils Coated with Acrylic Paint Containing TiO2 Nanoparticles","authors":"S. Armaković, Maria M. Savanović, Mirjana V. Šiljegović, Milica Kisić, Maja Šćepanović, M. Grujić-Brojčin, Nataša Simić, Lazar Gavanski, S. Armaković","doi":"10.3390/inorganics12010035","DOIUrl":"https://doi.org/10.3390/inorganics12010035","url":null,"abstract":"The study comprehensively investigates the design and performance of self-cleaning surfaces fabricated by coating aluminum foil with an acrylic paint matrix enriched with different content of titanium dioxide (TiO2) nanoparticles. The main goal was to assess the self-cleaning characteristics of the surfaces obtained. This study employs scanning electron microscopy (SEM) to analyze the morphology of TiO2-modified acrylic surfaces, revealing spherical particles. Raman spectroscopy elucidates signatures characterizing TiO2 incorporation within the acrylic matrix, providing comprehensive insights into structural and compositional changes for advanced surface engineering. Alternating current (AC) impedance spectroscopy was used to assess selected charge transport properties of produced self-cleaning surfaces, allowing us to gain valuable insights into the material’s conductivity and its potential impact on photocatalytic performance. The self-cleaning properties of these tiles were tested against three frequently used textile dyes, which are considered to pose a serious environmental threat. Subsequently, improving self-cleaning properties was achieved by plasma treatment, utilizing a continuous plasma arc. The plasma treatment led to enhanced charge separation and surface reactivity, crucial factors in the self-cleaning mechanism. To deepen our comprehension of the reactive properties of dye molecules and their degradation dynamics, we employed a combination of density functional tight binding (DFTB) and density functional theory (DFT) calculations. This investigation lays the foundation for advancing self-cleaning materials with extensive applications, from architectural coatings to environmental remediation technologies.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139606599","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 : 2024-01-18DOI: 10.20944/preprints202312.1414.v1
Audrey L. Heffner, N. Maio
Viruses rely on host cells to replicate their genomes and assemble new viral particles. Thus, they have evolved intricate mechanisms to exploit host factors. Host cells, in turn, have developed strategies to inhibit viruses, resulting in a nuanced interplay of co-evolution between virus and host. This dynamic often involves competition for resources crucial for both host cell survival and virus replication. Iron and iron-containing cofactors, including iron–sulfur clusters, are known to be a heavily fought for resource during bacterial infections, where control over iron can tug the war in favor of the pathogen or the host. It is logical to assume that viruses also engage in this competition. Surprisingly, our knowledge about how viruses utilize iron (Fe) and iron–sulfur (FeS) clusters remains limited. The handful of reviews on this topic primarily emphasize the significance of iron in supporting the host immune response against viral infections. The aim of this review, however, is to organize our current understanding of how viral proteins utilize FeS clusters, to give perspectives on what questions to ask next and to propose important avenues for future investigations.
{"title":"Tip of the Iceberg: A New Wave of Iron–Sulfur Cluster Proteins Found in Viruses","authors":"Audrey L. Heffner, N. Maio","doi":"10.20944/preprints202312.1414.v1","DOIUrl":"https://doi.org/10.20944/preprints202312.1414.v1","url":null,"abstract":"Viruses rely on host cells to replicate their genomes and assemble new viral particles. Thus, they have evolved intricate mechanisms to exploit host factors. Host cells, in turn, have developed strategies to inhibit viruses, resulting in a nuanced interplay of co-evolution between virus and host. This dynamic often involves competition for resources crucial for both host cell survival and virus replication. Iron and iron-containing cofactors, including iron–sulfur clusters, are known to be a heavily fought for resource during bacterial infections, where control over iron can tug the war in favor of the pathogen or the host. It is logical to assume that viruses also engage in this competition. Surprisingly, our knowledge about how viruses utilize iron (Fe) and iron–sulfur (FeS) clusters remains limited. The handful of reviews on this topic primarily emphasize the significance of iron in supporting the host immune response against viral infections. The aim of this review, however, is to organize our current understanding of how viral proteins utilize FeS clusters, to give perspectives on what questions to ask next and to propose important avenues for future investigations.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-01-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139614502","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 : 2024-01-16DOI: 10.3390/inorganics12010032
Anwar Abo-Amer, M. E. Moustafa, Paul D. Boyle, R. Puddephatt
The organoplatinum chemistry of the ligands 2-C5H4N-CH2-NH-C6H3-2-OH-5-X (L1, X = H; L3, X = NO2) and 2-C5H4N-CH=N-C6H3-2-OH-5-X (L2, X = H; L4, X = NO2), which contain an appended phenol substituent, is described. Comparisons are made between the ligands with amine or imine groups (L1, L3 vs. L2, L4) and ligands with X = H or NO2 (L1, L2 vs. L3, L4), and major differences are observed. Thus, on reaction with the cycloneophylplatinum(II) complex [{Pt(CH2CMe2C6H4)(μ-SMe2)}2], ligands L1, L2 and L4 give the corresponding platinum(II) complexes [Pt(CH2CMe2C6H4)(κ2-N,N′-L)], containing a Pt··HO hydrogen bond, whereas L3 gives a mixture of isomeric platinum(IV) hydride complexes [PtH(CH2CMe2C6H4)(κ3-N,N′,O-L3-H)], which are formed by oxidative addition of the phenol O-H bond and which react further with oxygen to give [Pt(OH)(CH2CMe2C6H4)(κ3-N,N′,O-L3-H)]. The differences in reactivity are proposed to be due to the greater acidity of the nitro-substituted phenol groups in L3 and L4 and to the greater ability of the deprotonated amine ligand L3 over L4 to stabilize platinum(IV) by adopting the fac-κ3-N,N′,O-L3-H coordination mode.
{"title":"Organoplatinum Chemistry Related to Alkane Oxidation: The Effect of a Nitro Substituent in Ligands Having an Appended Phenol Group","authors":"Anwar Abo-Amer, M. E. Moustafa, Paul D. Boyle, R. Puddephatt","doi":"10.3390/inorganics12010032","DOIUrl":"https://doi.org/10.3390/inorganics12010032","url":null,"abstract":"The organoplatinum chemistry of the ligands 2-C5H4N-CH2-NH-C6H3-2-OH-5-X (L1, X = H; L3, X = NO2) and 2-C5H4N-CH=N-C6H3-2-OH-5-X (L2, X = H; L4, X = NO2), which contain an appended phenol substituent, is described. Comparisons are made between the ligands with amine or imine groups (L1, L3 vs. L2, L4) and ligands with X = H or NO2 (L1, L2 vs. L3, L4), and major differences are observed. Thus, on reaction with the cycloneophylplatinum(II) complex [{Pt(CH2CMe2C6H4)(μ-SMe2)}2], ligands L1, L2 and L4 give the corresponding platinum(II) complexes [Pt(CH2CMe2C6H4)(κ2-N,N′-L)], containing a Pt··HO hydrogen bond, whereas L3 gives a mixture of isomeric platinum(IV) hydride complexes [PtH(CH2CMe2C6H4)(κ3-N,N′,O-L3-H)], which are formed by oxidative addition of the phenol O-H bond and which react further with oxygen to give [Pt(OH)(CH2CMe2C6H4)(κ3-N,N′,O-L3-H)]. The differences in reactivity are proposed to be due to the greater acidity of the nitro-substituted phenol groups in L3 and L4 and to the greater ability of the deprotonated amine ligand L3 over L4 to stabilize platinum(IV) by adopting the fac-κ3-N,N′,O-L3-H coordination mode.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139618305","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 : 2024-01-12DOI: 10.3390/inorganics12010029
Irena Kostova
Cancer is one of the leading causes of human death among all major diseases. Metal-based complexes are considered as the most promising vital part in the existing arsenal of cytotoxic candidates used in cancer therapy and diagnostics. The efforts of many scientific groups resulted in the development of numerous metal-based compounds featuring different biologically active organic ligands in order to modulate their bioactivity. Along with the main representatives as potential therapeutic agents, such as the complexes Pt(II)/Pt(IV), Pd(II), Ru(II)/Ru(III), Ag(I), Au(I)/Au(III), Ti(IV), V(IV) and Ga(III), many other transition metal and lanthanide complexes possessing antiproliferative activity are widely discussed in the literature. However, such drugs remain outside the scope of this review. The main purpose of the current study is to review the potential activity of main group metal- and metalloid-based complexes against the most common cancer cell types, such as carcinomas (lung, liver, breast, kidney, gastric, colorectal, bladder, ovarian, cervical, prostate, etc.); sarcomas; blastomas; lymphomas; multiple myeloma; and melanoma. Overcoming the long disregard of organometallic compounds of metals and metalloids from the main groups, a growing number of emerging anticancer agents remarkably prove this field offers an extensive variety of new options for the design of innovative unexplored chemopharmaceutics. Moreover, some of the metal complexes and organometallic compounds from these elements can exhibit entirely different, specific modes of action and biological targets. Obviously, exploitation of their distinct properties deserves more attention.
{"title":"Survey of Main Group Metals and Metalloids in Cancer Treatment","authors":"Irena Kostova","doi":"10.3390/inorganics12010029","DOIUrl":"https://doi.org/10.3390/inorganics12010029","url":null,"abstract":"Cancer is one of the leading causes of human death among all major diseases. Metal-based complexes are considered as the most promising vital part in the existing arsenal of cytotoxic candidates used in cancer therapy and diagnostics. The efforts of many scientific groups resulted in the development of numerous metal-based compounds featuring different biologically active organic ligands in order to modulate their bioactivity. Along with the main representatives as potential therapeutic agents, such as the complexes Pt(II)/Pt(IV), Pd(II), Ru(II)/Ru(III), Ag(I), Au(I)/Au(III), Ti(IV), V(IV) and Ga(III), many other transition metal and lanthanide complexes possessing antiproliferative activity are widely discussed in the literature. However, such drugs remain outside the scope of this review. The main purpose of the current study is to review the potential activity of main group metal- and metalloid-based complexes against the most common cancer cell types, such as carcinomas (lung, liver, breast, kidney, gastric, colorectal, bladder, ovarian, cervical, prostate, etc.); sarcomas; blastomas; lymphomas; multiple myeloma; and melanoma. Overcoming the long disregard of organometallic compounds of metals and metalloids from the main groups, a growing number of emerging anticancer agents remarkably prove this field offers an extensive variety of new options for the design of innovative unexplored chemopharmaceutics. Moreover, some of the metal complexes and organometallic compounds from these elements can exhibit entirely different, specific modes of action and biological targets. Obviously, exploitation of their distinct properties deserves more attention.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139624369","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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：