Inorganics

24 pages, 4160 KiB

Open AccessArticle

Exploring the Anti-Corrosion, Photocatalytic, and Adsorptive Functionalities of Biogenically Synthesized Zinc Oxide Nanoparticles

by Syed Najmul Hejaz Azmi and Mahboob Alam

Inorganics 2024, 12(7), 199; https://doi.org/10.3390/inorganics12070199 - 22 Jul 2024

Viewed by 512

Abstract

This study reported the synthesis of ZnO nanoparticles (ZnO NPs) using Cucurbita pepo L. seed extract and explored their multifunctional properties such as anti-corrosion, photocatalytic, and adsorption capabilities. The synthesized ZnO NPs were characterized by Fourier-transform infrared spectroscopy (FTIR) to identify their functional [...] Read more.

This study reported the synthesis of ZnO nanoparticles (ZnO NPs) using Cucurbita pepo L. seed extract and explored their multifunctional properties such as anti-corrosion, photocatalytic, and adsorption capabilities. The synthesized ZnO NPs were characterized by Fourier-transform infrared spectroscopy (FTIR) to identify their functional groups, thermogravimetric analysis (TGA) to assess their thermal stability, transmission electron microscopy (TEM), and scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDX) to determine their size, morphology, and elemental composition. The characterization of biofabricated ZnO NPs revealed an average particle size of 32.88 nm; however, SEM displayed a tendency for the particles to agglomerate. Furthermore, the X-ray diffraction (XRD) and EDX analysis confirmed the NPs as ZnO, matching patterns reported in the literature. In this study, the potential of the biogenic ZnO NPs was explored for multifunctional applications. Zinc oxide nanoparticles exhibited a higher capacity for adsorbing hydrogen sulfide (H₂S) compared to bulk zinc oxide, mostly because of their larger surface area. In addition, electrochemical studies demonstrated a substantial enhancement in the corrosion resistance of mild steel in a 1.0 M HCl solution. ZnO NPs also demonstrated remarkable photodegradation effectiveness, reducing 75% of methyl orange in 60 min under sun-light irradiation. This implies that they could be used to remediate organic pollutants (organic dyes) from wastewater. Full article

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10 pages, 7696 KiB

Open AccessArticle

A Novel Spinel High-Entropy Oxide (Cr_0.2Mn_0.2Co_0.2Ni_0.2Zn_0.2)₃O₄ as Anode Material for Lithium-Ion Batteries

by Changqing Jin, Yulong Wang, Haobin Dong, Yongxing Wei, Ruihua Nan, Zengyun Jian, Zhong Yang and Qingping Ding

Inorganics 2024, 12(7), 198; https://doi.org/10.3390/inorganics12070198 - 21 Jul 2024

Viewed by 369

Abstract

In this study, we synthesized spinel high-entropy oxide (HEO) (Cr_0.2Mn_0.2Co_0.2Ni_0.2Zn_0.2)₃O₄ nanoparticles by a simple solution combustion method. These particles were investigated for their performance as anodes in lithium-ion batteries. The [...] Read more.

In this study, we synthesized spinel high-entropy oxide (HEO) (Cr_0.2Mn_0.2Co_0.2Ni_0.2Zn_0.2)₃O₄ nanoparticles by a simple solution combustion method. These particles were investigated for their performance as anodes in lithium-ion batteries. The reversible capacity is 132 mAh·g⁻¹ after 100 cycles at a current density of 100 mA·g⁻¹, 107 mAh·g⁻¹ after 1000 cycles at a current density of 1 A g⁻¹, and 96 mAh·g⁻¹ rate capacity at a high current density of 2 A g⁻¹. The outstanding cycle stability under high current densities and remarkable rate performance can be attributed to the stable structure originating from the high entropy of the material. Full article

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

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10 pages, 2942 KiB

Open AccessCommunication

Novel Strategy to Evaluate Platinum Photocatalysts for Hydrosilation-Curable Silicones

by Melina Michailidis, John Leman and Peter J. Bonitatibus, Jr.

Inorganics 2024, 12(7), 197; https://doi.org/10.3390/inorganics12070197 - 21 Jul 2024

Viewed by 402

Abstract

UV-activated catalytic hydrosilation is a low-temperature crosslinking process that has attracted attention for its high efficiency and lower energy demand relative to thermal curing. In this study, formulations comprising industrially relevant model silanes and Pt photocatalysts trimethyl(methylcyclopentadienyl)platinum(IV) and trimethyl(pentamethylcyclopentadienyl)platinum(IV) (MeCpPtMe₃ and Cp*PtMe [...] Read more.

UV-activated catalytic hydrosilation is a low-temperature crosslinking process that has attracted attention for its high efficiency and lower energy demand relative to thermal curing. In this study, formulations comprising industrially relevant model silanes and Pt photocatalysts trimethyl(methylcyclopentadienyl)platinum(IV) and trimethyl(pentamethylcyclopentadienyl)platinum(IV) (MeCpPtMe₃ and Cp*PtMe₃, respectively) were prepared with and without a photosensitizer (PS) and assessed for catalytic performance by a novel strategy. Photopolymerizations were initiated using different wavelengths from LEDs and monitored in real-time using an Attenuated Total Reflectance-Fourier Transform Infrared (ATR-FTIR) “well” strategy to track the degree of cure in ultra-thin films by consumption of hydride via the disappearance of the Si-H bending absorption band at 915 cm⁻¹. Irradiation of formulations with 365 nm excitation showed higher conversions relative to 400 nm light and improvements to calculated initial reaction rates by incorporation of a PS suggested increased sensitization to 365 nm irradiation. To the best of our knowledge, this is the first study to report catalytic performance, electronic absorption spectroscopic data, and the crystal structure of Cp*PtMe₃. Full article

(This article belongs to the Section Organometallic Chemistry)

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8 pages, 1252 KiB

Open AccessArticle

La₂C₂@D₅(450)-C₁₀₀: Calculated High Energy Gain in Encapsulation

by Zdeněk Slanina, Filip Uhlík, Takeshi Akasaka, Xing Lu and Ludwik Adamowicz

Inorganics 2024, 12(7), 196; https://doi.org/10.3390/inorganics12070196 - 18 Jul 2024

Viewed by 309

Abstract

The structure and energetics of the clusterfullerene La₂C₂@

D_{5}

(450)-C₁₀₀ are calculated at the B3LYP/6-31G*∼SDD level (including counterpoise correction for the basis set superposition error), and the observed features are confirmed. Its stability is explained by substantial [...] Read more.

The structure and energetics of the clusterfullerene La₂C₂@

D_{5}

(450)-C₁₀₀ are calculated at the B3LYP/6-31G*∼SDD level (including counterpoise correction for the basis set superposition error), and the observed features are confirmed. Its stability is explained by substantial energy gain connected with the encapsulation, viz. 140 kcal/mol per atom of the encapsulate, actually higher than previously found for comparable systems. Full article

(This article belongs to the Special Issue Research on Metallofullerenes)

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18 pages, 1867 KiB

Open AccessArticle

Conformational, Electrochemical, and Antioxidative Properties of Conjugates of Different Ferrocene Turn-Inducing Scaffolds with Hydrophobic Amino Acids

by Monika Kovačević, Sunčica Roca, Dijana Jadreško, Jasna Mrvčić, Karla Hanousek Čiča, Mojca Čakić Semenčić and Lidija Barišić

Inorganics 2024, 12(7), 195; https://doi.org/10.3390/inorganics12070195 - 18 Jul 2024

Viewed by 341

Abstract

The incorporation of different ferrocene scaffolds into the peptide sequences induces the formation of hydrogen-bond-based secondary structural elements that are frequently observed in natural peptides and proteins. There are three simple ferrocene scaffolds for conjugation with amino acids and peptides that serve as [...] Read more.

The incorporation of different ferrocene scaffolds into the peptide sequences induces the formation of hydrogen-bond-based secondary structural elements that are frequently observed in natural peptides and proteins. There are three simple ferrocene scaffolds for conjugation with amino acids and peptides that serve as templates for ferrocene peptidomimetics, namely ferrocene-1,1′-dicarboxylic acid (Fcd, I), 1′-aminoferrocene-1-carboxylic acid (Fca, III), and ferrocene-1,1′-diamine (Fcda, V). Here, we have investigated their ability to induce the turn structure upon conjugation with Val, Leu, and Phe. Furthermore, we also wanted to determine whether the branched side chains of Val, Leu, and Phe interfere with intramolecular hydrogen bonding (IHB). For these purposes, we performed a detailed spectroscopic analysis by measuring the concentration, temperature, and solvent dependence of the IR, NMR, and CD spectra. The effect of the different ferrocene scaffolds on the antioxidant activity of the prepared peptides was tested using the DPPH and ABTS methods, and was further rationalized using electrochemical measurements. It was found that the ferrocene scaffold has the greatest influence on the hydrogen bonding pattern, while the influence of the side branches of the amino acids is less relevant. Full article

(This article belongs to the Special Issue Metal Complexes Diversity: Synthesis, Conformations, and Bioactivity)

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11 pages, 1400 KiB

Open AccessArticle

Crystal Structure and Anti-Proliferative and Mutagenic Evaluation of the Palladium(II) Complex of Deoxyalliin

by Tuany Zambroti Candido, Mariana Mazzo Quintanilha, Bianca Alves Schimitd, Déborah de Alencar Simoni, Douglas Hideki Nakahata, Raphael Enoque Ferraz de Paiva, Igor Henrique Cerqueira, Flávia Aparecida Resende, João Ernesto Carvalho, Ana Lucia Tasca Gois Ruiz, Carmen Silvia Passos Lima and Pedro Paulo Corbi

Inorganics 2024, 12(7), 194; https://doi.org/10.3390/inorganics12070194 - 18 Jul 2024

Viewed by 495

Abstract

Platinum(II) and palladium(II) complexes have been investigated as potential anticancer drugs since the serendipitous discovery of the antineoplastic activities of cisplatin in the 1960s. Skin cancer is considered the most common malignant neoplasm that affects humans, and melanoma is the most lethal type [...] Read more.

Platinum(II) and palladium(II) complexes have been investigated as potential anticancer drugs since the serendipitous discovery of the antineoplastic activities of cisplatin in the 1960s. Skin cancer is considered the most common malignant neoplasm that affects humans, and melanoma is the most lethal type of skin cancer. Surgical excision is the main form of treatment, which also may include radiotherapy, systemic chemotherapy, and immunotherapy. In this work, new insights concerning the structural characterization and in vitro anti-proliferative activity of the palladium(II) complex with the amino acid deoxyalliin (Pd-sac) against a panel of thirteen human tumor cells, with emphasis on skin cancer cell lines, are presented. The composition of the complex was confirmed by elemental analysis as [Pd(C₆H₁₀NO₂S)₂]. The structure of the complex was elucidated for the first time by a single-crystal X-ray diffraction technique. Each deoxyalliin molecule coordinates in a bidentate N,S-mode to palladium(II) in a trans-configuration analogous to the platinum(II) deoxyalliin complex early reported. As the main result, the Pd-sac complex showed a selective anti-proliferative activity against melanoma (UACC-62, TGI = 63.5 µM), while both deoxyalliin and K₂PdCl₄ were inactive against all cell lines. Moreover, Pd-sac did not affect the proliferation of non-tumorigenic keratinocytes (HaCaT, TGI > 586 µM) and was non-mutagenic in the Ames assay. The results open new perspectives for in vivo studies concerning the application of the Pd-sac complex in the treatment of melanoma. Full article

(This article belongs to the Special Issue Noble Metals in Medicinal Inorganic Chemistry)

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21 pages, 15568 KiB

Open AccessReview

Metalloborospherene Analogs to Metallofullerene

by Jordan Burkhardt, Hayden Prescott and Wan-Lu Li

Inorganics 2024, 12(7), 193; https://doi.org/10.3390/inorganics12070193 - 17 Jul 2024

Viewed by 576

Abstract

Boron, the neighbor element to carbon in the periodic table, is characterized by unique electron deficiency that fosters multicenter delocalized bonding, contributing to its diverse chemistry. Unlike carbon cages (fullerenes), which preserve their structural integrity under endohedral or exohedral doping, larger boron cages [...] Read more.

Boron, the neighbor element to carbon in the periodic table, is characterized by unique electron deficiency that fosters multicenter delocalized bonding, contributing to its diverse chemistry. Unlike carbon cages (fullerenes), which preserve their structural integrity under endohedral or exohedral doping, larger boron cages (borospherenes) exhibit diverse structural configurations. These configurations can differ from those of pure boron cages and are stabilized by various metals through unique metal–boron bonding, resulting in a variety of metalloborospherenes. Due to boron’s electron deficiency, metalloborospherenes exhibit fascinating chemical bonding patterns that vary with cluster size and the type of metal dopants. This review paper highlights recent advancements in metalloborospherene research, drawing comparisons with metallofullerenes, and focuses on the use of transition metals, lanthanides, and actinides as dopants across various cage dimensions. Full article

(This article belongs to the Special Issue Research on Metallofullerenes)

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13 pages, 2146 KiB

Open AccessArticle

Exploring the Nature of Ag–Ag Interactions in Different Tellurides by Means of the Crystal Orbital Bond Index (COBI)

by Leander Weinelt and Simon Steinberg

Inorganics 2024, 12(7), 192; https://doi.org/10.3390/inorganics12070192 - 12 Jul 2024

Viewed by 538

Abstract

Over the decades, intensive explorations have been conducted to understand the nature of d¹⁰−d¹⁰ interactions. The recent establishment of a bonding indicator named the crystal orbital bond index stimulated our impetus to probe the capabilities of that approach for the [...] Read more.

Over the decades, intensive explorations have been conducted to understand the nature of d¹⁰−d¹⁰ interactions. The recent establishment of a bonding indicator named the crystal orbital bond index stimulated our impetus to probe the capabilities of that approach for the examples of Ag–Ag interactions in different tellurides. In the framework of our quantum chemical explorations, we inspected the electronic structures of two tellurides which were previously reported to comprise d¹⁰−d¹⁰ interactions, while the third candidate material, i.e., RbCe₂Ag₃Te₅, has been obtained from reactions of rubidium chloride, cerium, silver and tellurium for the very first time. The outcome of our explorations clearly shows that the nature of Ag–Ag interactions is well mirrored by the corresponding COBI. Full article

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26 pages, 8101 KiB

Open AccessArticle

Enhanced Removal of Rhodamine b Dye from Aqueous Media via Adsorption on Facilely Synthesized Zinc Ferrite Nanoparticles

by Asma S. Al-Wasidi and Salwa AlReshaidan

Inorganics 2024, 12(7), 191; https://doi.org/10.3390/inorganics12070191 - 12 Jul 2024

Viewed by 536

Abstract

This paper studies the synthesis, characterization, and application of ZnFe₂O₄ nanoparticles for the removal of rhodamine b dye from aqueous media. Utilizing the combustion procedure, ZnFe₂O₄ nanoparticles were synthesized using two different fuels: glutamine (SG) and L-arginine [...] Read more.

This paper studies the synthesis, characterization, and application of ZnFe₂O₄ nanoparticles for the removal of rhodamine b dye from aqueous media. Utilizing the combustion procedure, ZnFe₂O₄ nanoparticles were synthesized using two different fuels: glutamine (SG) and L-arginine (SA). In addition, the synthesized ZnFe₂O₄ nanoparticles were characterized through various techniques, including Fourier transform infrared (FTIR), X-ray diffraction (XRD), field emission scanning electron microscope (FE-SEM), energy-dispersive X-ray (EDX), high resolution transmission electron microscope (HR-TEM), and Brunauer-Emmett-Teller (BET) surface area analysis. XRD analysis verified the creation of a ZnFe₂O₄ cubic spinel structure without any contaminants, revealing average crystallite sizes of 43.72 and 29.38 nm for the SG and SA samples, respectively. The FTIR spectra exhibited peaks indicative of metal-oxygen bond stretching, verifying the presence of a spinel formation. Elemental analysis via EDX confirmed the stoichiometric composition typical of zinc ferrite. In addition, FE-SEM imaging displayed that the SG and SA samples are composed of particles with irregular and spherical shapes, measuring average diameters of 135.11 and 59.89 nm, respectively. Furthermore, the BET surface area of the SG and SA samples is 60 and 85 m²/g, respectively. The maximum adsorption capacity of the SA sample (409.84 mg/g) towards rhodamine b dye was higher than that of the SG sample (279.33 mg/g), which was ascribed to its larger surface area and porosity. Kinetic and equilibrium studies revealed that the adsorption process of rhodamine b dye onto the SG and SA samples followed the Langmuir isotherm and pseudo-second-order model. Thermodynamic analysis indicated that the adsorption process was spontaneous, exothermic, and physical. The study concludes that ZnFe₂O₄ nanoparticles synthesized using L-arginine (SA) exhibit enhanced rhodamine b dye removal efficiency due to their smaller size, increased surface area, and higher porosity compared to those synthesized with glutamine (SG). The optimum conditions for the adsorption process of rhodamine b dye were found to be at pH 10, a contact time of 70 min, and a temperature of 298 K. These findings underscore the potential of L-arginine-synthesized ZnFe₂O₄ nanoparticles for effective and sustainable environmental cleanup applications. Full article

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25 pages, 8615 KiB

Open AccessReview

Recent Advances in Metal Complexes Based on Biomimetic and Biocompatible Organic Ligands against Leishmaniasis Infections: State of the Art and Alternatives

by Sandra Jimenez-Falcao and Jose Manuel Mendez-Arriaga

Inorganics 2024, 12(7), 190; https://doi.org/10.3390/inorganics12070190 - 12 Jul 2024

Viewed by 649

Abstract

Leishmaniasis is a complex disease present in a variety of manifestations listed by the World Health Organization (WHO) as one of the neglected diseases with a worse prognosis if not treated. Medicinal inorganic chemistry has provided a variety of drugs based on metal–organic [...] Read more.

Leishmaniasis is a complex disease present in a variety of manifestations listed by the World Health Organization (WHO) as one of the neglected diseases with a worse prognosis if not treated. Medicinal inorganic chemistry has provided a variety of drugs based on metal–organic complexes synthesized with different metal centers and organic ligands to fight against a great number of parasite maladies and specifically Leishmaniasis. Taking advantage of the natural properties that many metals present for biotechnological purposes, nanotechnology has offered, in recent years, a new approach consisting on the application of metal nanoparticles to treat a great number of parasitic diseases, as a drug vehicle or as a treatment themselves. The aim of this review is to gather the most widely used metal complexes and metallic nanoparticles and the most recent strategies proposed as antileishmanial agents. Full article

(This article belongs to the Special Issue Recent Advances in Biological and Catalytic Applications of Metal Complexes)

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23 pages, 8826 KiB

Open AccessArticle

Synthesis, Characterization, DNA, Fluorescence, Molecular Docking, and Antimicrobial Evaluation of Novel Pd(II) Complex Containing O, S Donor Schiff Base Ligand and Azole Derivative

by Maged S. Al-Fakeh, Muneera Alrasheedi, Ard Elshifa M. E. Mohammed, Ahmed B. M. Ibrahim, Sadeq M. Al-Hazmy, Ibrahim A. Alhagri and Sabri Messaoudi

Inorganics 2024, 12(7), 189; https://doi.org/10.3390/inorganics12070189 - 11 Jul 2024

Viewed by 491

Abstract

Pd(II) with the Schiff base ligand 2-Hydroxy-3-Methoxy Benzaldehyde-Thiosemicarbazone (HMBATSC) (L2) and 2-aminobenzothiazole (2-ABZ) (L1) was synthesized. The Schiff base ligand and the Palladium(II) complex were characterized by C.H.N.S, FT-IR, conductance studies, magnetic susceptibility, XRD, and TGA. From the elemental analysis and spectral data, [...] Read more.

Pd(II) with the Schiff base ligand 2-Hydroxy-3-Methoxy Benzaldehyde-Thiosemicarbazone (HMBATSC) (L2) and 2-aminobenzothiazole (2-ABZ) (L1) was synthesized. The Schiff base ligand and the Palladium(II) complex were characterized by C.H.N.S, FT-IR, conductance studies, magnetic susceptibility, XRD, and TGA. From the elemental analysis and spectral data, the complex was proposed to have the formula [Pd(HMBATSC)(2-ABZ)H₂O]. The interaction between the Pd(II) complex and DNA was examined through various methods, including UV–Vis spectroscopy, fluorescence techniques, and DNA viscosity titrations. The findings provided strong evidence that the interaction between the Pd(II) complex and DNA occurs through the intercalation mode. The analysis yielded the following values: a Stern–Volmer quenching constant (k_sv) of 1.67 × 10⁴ M⁻¹, a quenching rate constant (k_q) of 8.35 × 10¹¹ M⁻¹ s⁻¹, a binding constant (k_b) of 5.20 × 10⁵ M⁻¹, and a number of binding the sites (n) of 1.392. DFT studies suggest that the azole derivative may act as an electron donor through pyridine nitrogen, while the Schiff base ligand may act as an electron donor via oxygen and sulfur atoms. TDDFT calculations indicate that the intramolecular charge transfer from the Schiff base to Pd(II) is responsible for the complex’s fluorescence quenching. The powder X-ray diffraction data revealed that the complex is arranged in a monoclinic system. The resulting Pd(II) complex was investigated for its antimicrobial activity and demonstrated antibacterial efficiency. Interestingly, it showed potent activity against E. coli and E. niger that was found to be more powerful than that recorded for Neomycin. Full article

(This article belongs to the Special Issue Noble Metals in Medicinal Inorganic Chemistry)

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12 pages, 3850 KiB

Open AccessArticle

Cu-Doped TiO₂ Thin Films by Spin Coating: Investigation of Structural and Optical Properties

by Syrine Sassi, Amal Bouich, Anouar Hajjaji, Lotfi Khezami, Brahim Bessais and Bernabé Mari Soucase

Inorganics 2024, 12(7), 188; https://doi.org/10.3390/inorganics12070188 - 8 Jul 2024

Viewed by 499

Abstract

Cu-doped TiO₂ films were synthesized directly on FTO glass with a spin coating method. With a variation in copper amount, samples were prepared with 0%, 1%, 2%, 4% and 8% of dopant concentrations. Morphological and structural characterization of undoped and Cu-doped TiO [...] Read more.

Cu-doped TiO₂ films were synthesized directly on FTO glass with a spin coating method. With a variation in copper amount, samples were prepared with 0%, 1%, 2%, 4% and 8% of dopant concentrations. Morphological and structural characterization of undoped and Cu-doped TiO₂ samples were investigated and the obtained results showed the small, spherical shapes of the nanoparticles forming a thin film on top of FTO glass and their preferred orientation of TiO₂ anatase (101), which is the same for each sample. However, this peak exhibited a slight shift for the 2% sample, related to the inflation of the microstrain compared to the other samples. For the optical properties, the 4% sample displayed the highest transmittance whereas the 2% sample exhibited the lowest band gap energy of 2.96 eV. Moreover, the PL intensity seems to be at its highest for the 2% sample due to the present peaking defects in the structure, whereas the 8% sample shows a whole new signal that is related to copper oxide. These properties make this material a potential candidate to perform as an electron transport layer (ETL) in solar cells and enhance their power conversion efficiency. Full article

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

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11 pages, 2302 KiB

Open AccessArticle

Synthesis of Tris(trifluoromethyl)nickelates(II)—Coping with “The C₂F₅ Problem”

by Sascha A. Schäfer, Rose Jordan, Katharina M. Klupsch, Felix Carl-Heinz Herwede and Axel Klein

Inorganics 2024, 12(7), 187; https://doi.org/10.3390/inorganics12070187 - 5 Jul 2024

Viewed by 501

Abstract

When synthesizing the versatile precursors (NMe₄)[Ni(CF₃)₃(MeCN)] we recently encountered the problem that marked amounts of C₂F₅ were incorporated instead of CF₃ under the chosen reaction conditions forming mixed-ligand nickelates [Ni(CF₃)x(C₂ [...] Read more.

When synthesizing the versatile precursors (NMe₄)[Ni(CF₃)₃(MeCN)] we recently encountered the problem that marked amounts of C₂F₅ were incorporated instead of CF₃ under the chosen reaction conditions forming mixed-ligand nickelates [Ni(CF₃)x(C₂F₅)y(MeCN)]⁻ (x + y = 3). We studied the three products with y = 0, 1, or 2, using ¹⁹F nuclear magnetic resonance (NMR) spectroscopy and single-crystal X-ray diffraction. We were able to trace the reaction mechanism and solve the problem by modifying the experimental conditions. Full article

(This article belongs to the Special Issue State-of-the-Art Inorganic Chemistry in Germany)

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63 pages, 7584 KiB

Open AccessReview

A Review of Ionic Liquids and Their Composites with Nanoparticles for Electrochemical Applications

by José Pereira, Reinaldo Souza and Ana Moita

Inorganics 2024, 12(7), 186; https://doi.org/10.3390/inorganics12070186 - 3 Jul 2024

Viewed by 777

Abstract

The current study focuses on reviewing the actual progress of the use of ionic liquids and derivatives in several electrochemical application. Ionic liquids can be prepared at room temperature conditions and by including a solution that can be a salt in water, or [...] Read more.

The current study focuses on reviewing the actual progress of the use of ionic liquids and derivatives in several electrochemical application. Ionic liquids can be prepared at room temperature conditions and by including a solution that can be a salt in water, or a base or acid, and are composed of organic cations and many charge-delocalized organic or inorganic anions. The electrochemical properties, including the ionic and electronic conductivities of these innovative fluids and hybrids, are addressed in depth, together with their key influencing parameters including type, fraction, functionalization of the nanoparticles, and operating temperature, as well as the incorporation of surfactants or additives. Also, the present review assesses the recent applications of ionic liquids and corresponding hybrids with the addition of nanoparticles in diverse electrochemical equipment and processes, together with a critical evaluation of the related feasibility concerns in different applications. Those ranging from the metal-ion batteries, in which ionic liquids possess a prominent role as electrolytes and reference electrodes passing through the dye of sensitized solar cells and fuel cells, to finishing processes like the ones related with low-grade heat harvesting and supercapacitors. Moreover, the overview of the scientific articles on the theme resulted in the comparatively brief examination of the benefits closely linked with the use of ionic fluids and corresponding hybrids, such as improved ionic conductivity, thermal and electrochemical stabilities, and tunability, in comparison with the traditional solvents, electrolytes, and electrodes. Finally, this work analyzes the fundamental limitations of such novel fluids such as their corrosivity potential, elevated dynamic viscosity, and leakage risk, and highlights the essential prospects for the research and exploration of ionic liquids and derivatives in various electrochemical devices and procedures. Full article

(This article belongs to the Special Issue Advanced Electrode Materials for Energy Storage Devices)

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20 pages, 25294 KiB

Open AccessArticle

Effect of Impregnation of PEDOT:PSS in Etched Aluminium Electrodes on the Performance of Solid State Electrolytic Capacitors

by Néstor Calabia Gascón, Benny Wouters, Herman Terryn and Annick Hubin

Inorganics 2024, 12(7), 185; https://doi.org/10.3390/inorganics12070185 - 2 Jul 2024

Viewed by 413

Abstract

Electrolytic capacitors store larger amounts of energy thanks to their thin dielectric layers and enlarged surface area. However, the benefits of using a liquid electrolyte are at the expense of the possibility of leakage, evaporation, or rupture of the device over time. As [...] Read more.

Electrolytic capacitors store larger amounts of energy thanks to their thin dielectric layers and enlarged surface area. However, the benefits of using a liquid electrolyte are at the expense of the possibility of leakage, evaporation, or rupture of the device over time. As a solution, solid electrolytes, such as conductive polymers, substitute the liquid ones decreasing the internal resistance and enlarging the lifetime of these devices. PEDOT:PSS is a widely used conductive polymer in the formation of solid electrolytic capacitors. However, using the enlarged surface of the porous electrodes efficiently requires industrial processes, the efficacy of which has not been explored. In this work, porous aluminium electrodes with dielectric layers of different thicknesses were coated with PEDOT:PSS at different levels of doping in order to study the efficiency of the production of solid electrolytic capacitors in industry. The combination of odd random phase electrochemical impedance spectroscopy (ORP-EIS) with surface characterization techniques (SEM-EDX, GDOES) formed a methodology that allowed the study of both the electrical properties and the level of impregnation for these model systems. All samples consisting of a porous aluminium electrode with an amount of PEDOT:PSS deposited on top resulted in an inefficient degree of penetration between the two electrodes. However, the electrochemical analysis proved that the use of dopants produces systems with the highest capacitive properties. Consequently, the evolution towards better solid electrolytic capacitors does not rely solely on the proper coverage of the porous electrodes, but on the proper electrical properties of the PEDOT:PSS within the pores. Full article

(This article belongs to the Special Issue Recent Advances in Energy Storage and Conversion)

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14 pages, 1827 KiB

Open AccessArticle

The Synthesis and Pharmacokinetics of a Novel Liver-Targeting Cholic Acid-Conjugated Carboplatin in Rats

by Yinyin Lan, Fuguo Han, Anli Gao, Xuemei Fan, Yanli Hao, Zhao Wang, Weiping Liu, Jing Jiang and Qingfei Liu

Inorganics 2024, 12(7), 184; https://doi.org/10.3390/inorganics12070184 - 30 Jun 2024

Viewed by 448

Abstract

A novel cholic acid-conjugated carboplatin (CP-CA) is developed as a liver-targeting prodrug of carboplatin (CP) for liver cancer. Instead of using CP as a raw material, CP-CA was synthesized simultaneously. This paper is focused on the comparison of CP-CA and CP with respect [...] Read more.

A novel cholic acid-conjugated carboplatin (CP-CA) is developed as a liver-targeting prodrug of carboplatin (CP) for liver cancer. Instead of using CP as a raw material, CP-CA was synthesized simultaneously. This paper is focused on the comparison of CP-CA and CP with respect to their pharmacokinetic (PK) and tissue distribution profiles in rats after their intravenous administration. Additionally, their uptake by human liver tumor cell Huh7 and normal human liver cell HL7702 are investigated. The inductively coupled plasma mass spectrometry (ICP-MS) method is applied for the determination of platinum in plasma, tissues, and cells. The PK results show that both the AUC_0–t and AUC_0–∞ data on Pt for CP-CA are significantly higher than those for CP (p < 0.01), indicating that the plasma exposure of CP-CA is significantly higher than that of CP. The CL₁, Vd₁, and Vd₂ data on Pt for CP-CA are significantly lower than those for CP (p < 0.01), while the MRT_0–t is significantly higher (p < 0.01), which is possibly related to a higher PPBR, and can strongly support the higher AUC_0–t and AUC_0–∞ of Pt for CP-CA compared to for CP. The tissue distribution results show that CP-CA is mainly distributed and accumulated in the liver after its intravenous administration to rats, revealing its liver-targeting profile. Compared to CP, CP-CA is more easily taken up by human liver cancer cells and normal human liver cells. The results suggest that CP-CA has a potential for further development as a new prodrug specific to liver cancer. Full article

(This article belongs to the Section Bioinorganic Chemistry)

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19 pages, 5723 KiB

Open AccessArticle

Synthesis of TiO₂/SBA-15 Nanocomposites by Hydrolysis of Organometallic Ti Precursors for Photocatalytic NO Abatement

by Ons El Atti, Julie Hot, Katia Fajerwerg, Christian Lorber, Bénédicte Lebeau, Andrey Ryzhikov, Myrtil Kahn, Vincent Collière, Yannick Coppel, Nicolas Ratel-Ramond, Philippe Ménini and Pierre Fau

Inorganics 2024, 12(7), 183; https://doi.org/10.3390/inorganics12070183 - 29 Jun 2024

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Abstract

The development of advanced photocatalysts for air pollution removal is essential to improve indoor air quality. TiO₂/mesoporous silica SBA-15 nanocomposites were synthesized using an organometallic decoration method, which leverages the high reactivity of Ti precursors to be hydrolyzed on the surface [...] Read more.

The development of advanced photocatalysts for air pollution removal is essential to improve indoor air quality. TiO₂/mesoporous silica SBA-15 nanocomposites were synthesized using an organometallic decoration method, which leverages the high reactivity of Ti precursors to be hydrolyzed on the surface water groups of silica supports. Both lab-made Ti(III) amidinate and commercial Ti(IV) amino precursors were utilized to react with water-rich SBA-15, obtained through a hydration process. The hydrated SBA-15 and the TiO₂/SBA-15 nanocomposites were characterized using TGA, FTIR, ¹H and ²⁹Si NMR, TEM, SEM, N₂ physisorption, XRD, and WAXS. This one-step TiO₂ decoration method achieved a loading of up to 51.5 wt.% of approximately 9 nm anatase particles on the SBA-15 surface. This structuring provided excellent accessibility of TiO₂ particles for photocatalytic applications under pollutant gas and UV-A light exposure. The combination with the high specific surface area of SBA-15 resulted in the efficient degradation of 400 ppb of NO pollutant gas. Due to synergistic effects, the best nanocomposite in this study demonstrated a NO abatement performance of 4.0% per used mg of TiO₂, which is 40% more efficient than the reference photocatalytic material TiO₂ P-25. Full article

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

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42 pages, 11578 KiB

Open AccessReview

Halide Perovskites’ Multifunctional Properties: Coordination Engineering, Coordination Chemistry, Electronic Interactions and Energy Applications beyond Photovoltaics

by Taame Abraha Berhe, Wei-Nien Su and Bing Joe Hwang

Inorganics 2024, 12(7), 182; https://doi.org/10.3390/inorganics12070182 - 28 Jun 2024

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Abstract

Halide perovskite materials have gained enormous attention for their semiconducting properties, higher power conversion efficiency and potential applications in a wide range of fields of study, along with their two key limitations: stability and toxicity. Despite great progress made on halide perovskites and [...] Read more.

Halide perovskite materials have gained enormous attention for their semiconducting properties, higher power conversion efficiency and potential applications in a wide range of fields of study, along with their two key limitations: stability and toxicity. Despite great progress made on halide perovskites and many promising research developments, the issues of stability and toxicity have not been fully resolved. Therefore, the coordination engineering of a new framework to obtain alternative new halide perovskite materials and a fundamental understanding of the coordination chemistry and electronic interactions forming the structure of these newly engineered halide perovskite materials are possible ways to overcome the issues related to both stability and toxicity. In this review, we comprehensively review the current development of halide perovskite families, both lead halide perovskites and lead-free halide perovskites, followed by the coordination engineering of the new frameworks to engineer new halide perovskite materials. All concerns regarding the fundamental ideas of coordination chemistry and electronic interactions are vital in forming halide perovskite structures and thus form the main aim of this review. We also discuss recent potential energy applications beyond photovoltaics and thus answer an essential and open question, ‘what could happen in the future of halide perovskites?’ in order to excite commercial enterprises and research institutions again as well as to motivate new predictions on the future continuity of this field. Full article

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20 pages, 5623 KiB

Open AccessArticle

Cost Optimization of Graphene Oxide-Modified Ultra-High-Performance Concrete Based on Machine Learning Methods

by Hui Lv, Mingfeng Du, Zijian Li, Li Xiao and Shuai Zhou

Inorganics 2024, 12(7), 181; https://doi.org/10.3390/inorganics12070181 - 28 Jun 2024

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Abstract

The use of carbon nanomaterials in ultra-high-performance concrete (UHPC) to improve its mechanical properties and durability is growing. Graphene oxide (GO) has emerged as one of the most promising nanomaterials in recent years for enhancing the properties of UHPC. The majority of research [...] Read more.

The use of carbon nanomaterials in ultra-high-performance concrete (UHPC) to improve its mechanical properties and durability is growing. Graphene oxide (GO) has emerged as one of the most promising nanomaterials in recent years for enhancing the properties of UHPC. The majority of research so far has been on the properties of UHPC enhanced with GO, but its high cost has limited its application in engineering. This work suggests a machine learning (ML)-based approach to optimize the mix ratio in order to lower the cost of graphene oxide-modified UHPC. To do this, an artificial neural network (ANN) is used to create the prediction model for the 28-day compressive strength and slump flow of UHPC. The performance of this model is then compared using nine different ML techniques. Subsequently, considering the restrictions of the UHPC component content, component proportion, and absolute volume, a genetic algorithm (GA) is adopted to lower the UHPC cost. The sensitivity analysis is carried out in the end. This study’s findings indicate that there is a decent degree of prediction accuracy since the difference between the ANN model’s predictions and the experimental outcomes is just 10%. The cost of UHPC optimized by GA is reduced to 776 $/m³, significantly lower than the average cost of UHPC. Full article

(This article belongs to the Special Issue Carbon Nanomaterials for Advanced Technology)

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13 pages, 3797 KiB

Open AccessArticle

Utilizing Biomolecule-Rich Citrus Fruit Waste as a Medium for the Eco-Friendly Preparation of Silver Nanoparticles with Antimicrobial Properties

by Ramesa Shafi Bhat, Abeer M. Al-Dbass, Arwa Ishaq A. Khayyat and Sooad Al-Daihan

Inorganics 2024, 12(7), 180; https://doi.org/10.3390/inorganics12070180 - 28 Jun 2024

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Abstract

An ample amount of fruit waste is generated as agro-industrial waste, leading to significant nutritional, economic, and environmental challenges. Fruit peels are rich in many valuable bioactive compounds with the potential for developing nanoparticles. This study examined fresh juices of two citrus fruit [...] Read more.

An ample amount of fruit waste is generated as agro-industrial waste, leading to significant nutritional, economic, and environmental challenges. Fruit peels are rich in many valuable bioactive compounds with the potential for developing nanoparticles. This study examined fresh juices of two citrus fruit peel wastes (Citrus sinensis: C. sinesis and Citrus limon: C. limon) for antioxidants and total protein. Then, we investigated their ability to produce silver nanoparticles, which were further analyzed for anti-microbial activity against thirteen pathogenic microbes. Both Citrus peel juices were rich in secondary metabolites. The formation of Ag nanoparticles was initially confirmed by UV-vis spectroscopy, with peaks at 400 nm for C. sinensis peel Ag nanoparticles and 430 nm for C. limon peel Ag nanoparticles. Further characterization was conducted using zeta sizer, zeta potential, Transmission Electron Microscopy (TEM), Scanning Electron Microscope (SEM), Energy-dispersive X-ray spectroscopy (EDX) and Fourier transform infrared (FTIR) spectroscopy. The antimicrobial activity was tested using the well diffusion method against 11 bacterial strains (five Gram-positive and six Gram-negative) and two fungal strains of Candida. TEM and SEM results revealed a spherical shape, with an average diameter of about 13 nm for C. sinensis and 21 nm for C. limon Ag. EDX confirmed the presence of silver in both nanoparticles. The FTIR spectrum of the extract indicated the presence of biomolecules, which facilitated the reduction and capping of the synthesized Ag nanoparticles. The prepared nanoparticles showed remarkable antimicrobial activity, but the nanoparticles from C. sinensis exhibited stronger antibacterial properties because of their smaller size. Citrus peel waste is a suitable medium for the eco-friendly production of silver nanoparticles. Full article

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13 pages, 3547 KiB

Open AccessArticle

Unraveling the Crystal Structure of Sodium Tetrabenzylborate: Synthesis through the Sodium Borohydride Reduction of Benzaldehyde in the Solid State

by Carlos A. Castilla-Martinez, Dominique Granier, Pascal G. Yot and Umit B. Demirci

Inorganics 2024, 12(7), 179; https://doi.org/10.3390/inorganics12070179 - 27 Jun 2024

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Abstract

We present the synthesis, characterization, and crystal structure of sodium tetrabenzylborate, a novel tetraalkoxyborate obtained via a direct mechanochemical reaction between benzaldehyde and sodium borohydride at room temperature. The molecular and crystal structures of this borate were investigated using ¹¹B MAS NMR, [...] Read more.

We present the synthesis, characterization, and crystal structure of sodium tetrabenzylborate, a novel tetraalkoxyborate obtained via a direct mechanochemical reaction between benzaldehyde and sodium borohydride at room temperature. The molecular and crystal structures of this borate were investigated using ¹¹B MAS NMR, IR spectroscopy, differential scanning calorimetry (DSC), and X-ray diffraction (XRD) analyses. Crystalline sodium tetrabenzylborate exists in two different crystal structures, which were elucidated using powder- and single-crystal-XRD analyses. At a low temperature (e.g., −100 °C), sodium tetrabenzylborate crystallizes in the monoclinic system with the space group P2₁ (No. 4), but at room temperature, it displays a crystallization in the tetragonal system with the space group

I \bar{4}

(No. 82). According to the DSC analysis, the phase transition occurs at −45 °C. Upon hydrolysis, sodium tetrabenzylborate undergoes direct transformation into benzyl alcohol, thereby confirming the ability of sodium borohydride to convert an aldehyde into its primary alcohol analog. The key findings from our analyses are presented herein. Full article

(This article belongs to the Section Inorganic Materials)

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23 pages, 5148 KiB

Open AccessReview

Research Progress of TiO₂ Modification and Photodegradation of Organic Pollutants

by Tan Mao, Junyan Zha, Ying Hu, Qian Chen, Jiaming Zhang and Xueke Luo

Inorganics 2024, 12(7), 178; https://doi.org/10.3390/inorganics12070178 - 26 Jun 2024

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Abstract

Titanium dioxide (TiO₂) photocatalysts, characterized by exceptional photocatalytic activity, high photoelectric conversion efficiency, and economic viability, have found widespread application in recent years for azo dye degradation. However, inherent constraints, such as the material’s limited visible light absorption stemming from its [...] Read more.

Titanium dioxide (TiO₂) photocatalysts, characterized by exceptional photocatalytic activity, high photoelectric conversion efficiency, and economic viability, have found widespread application in recent years for azo dye degradation. However, inherent constraints, such as the material’s limited visible light absorption stemming from its bandgap and the swift recombination of charge carriers, have impeded its broader application potential. Encouragingly, these barriers can be mitigated through the modification of TiO₂. In this review, the common synthesis methods of TiO₂ are reviewed, and the research progress of TiO₂ modification technology at home and abroad is discussed in detail, including precious metal deposition, transition metal doping, rare earth metal doping, composite semiconductors, and composite polymers. These modification techniques effectively enhance the absorption capacity of TiO₂ in the visible region and reduce the recombination rate of carriers and electrons, thus significantly improving its photocatalytic performance. Finally, this paper looks forward to the future development direction of TiO₂ photocatalytic materials, including the exploration of new modified materials, in-depth mechanism research, and performance optimization in practical applications, to provide useful references for further research and application of TiO₂ photocatalytic materials. Full article

(This article belongs to the Special Issue New Advances into Nanostructured Oxides, 2nd Edition)

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22 pages, 4753 KiB

Open AccessArticle

Synthesis, Characterization, and Cytotoxicity of a Ga(III) Complex with Warfarin

by Hubert Joe, Venceslava Atanasova, Jan Mojžiš and Irena Kostova

Inorganics 2024, 12(7), 177; https://doi.org/10.3390/inorganics12070177 - 24 Jun 2024

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Abstract

The gallium(III) complex of warfarin was synthesized, and its structure was determined by means of theoretical, analytical, and spectral analyses. Significant differences in the IR and Raman spectra of the complex were observed as compared to the spectra of the ligand and confirmed [...] Read more.

The gallium(III) complex of warfarin was synthesized, and its structure was determined by means of theoretical, analytical, and spectral analyses. Significant differences in the IR and Raman spectra of the complex were observed as compared to the spectra of the ligand and confirmed the suggested metal-ligand binding mode. The theoretical study of the Ga(III) complex of warfarin has been done to elucidate the structure-activity relation, inter- and intra-molecular interactions, and frontier molecular orbital energy analysis based on DFT computations. A molecular docking study has been performed to predict the biological activity of the molecule. In this paper, we report preliminary results about the cytotoxicity of the investigated compounds. The cytotoxic effects of the ligand and its Ga(III) complex were determined using the MTT method on different tumor cell lines. The screening performed revealed that the tested compounds exerted cytotoxic activity on the evaluated cell lines. Full article

(This article belongs to the Section Bioinorganic Chemistry)

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18 pages, 7714 KiB

Open AccessArticle

Synthesis, X-ray Structure, Cytotoxic, and Anti-Microbial Activities of Zn(II) Complexes with a Hydrazono s-Triazine Bearing Pyridyl Arm

by MennaAllah Hassan, Ayman El-Faham, Assem Barakat, Matti Haukka, Rajendhraprasad Tatikonda, Morsy A. M. Abu-Youssef, Saied M. Soliman and Amal Yousri

Inorganics 2024, 12(7), 176; https://doi.org/10.3390/inorganics12070176 - 21 Jun 2024

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Abstract

The [ZnL(ONO₂)₂] 1 and [ZnL(NCS)₂] 2 complexes were synthesized using self-assembly of the s-triazine tridentate ligand (L) with Zn(NO₃)₂·6H₂O and Zn(ClO₄)₂·6H₂O/NH₄ [...] Read more.

The [ZnL(ONO₂)₂] 1 and [ZnL(NCS)₂] 2 complexes were synthesized using self-assembly of the s-triazine tridentate ligand (L) with Zn(NO₃)₂·6H₂O and Zn(ClO₄)₂·6H₂O/NH₄SCN, respectively. The Zn(II) is further coordinated by two nitrate and two isothiocyanate groups as monodentate ligands in 1 and 2, respectively. Both complexes have distorted square pyramidal coordination environments where the extent of distortion is found to be greater in 2 (τ₅ = 0.41) than in 1 (τ₅ = 0.28). Hirshfeld calculations explored the significant C···O, C···C, N···H, and O···H contacts in the molecular packing of both complexes. The energy framework analysis gave the total interaction energies of −317.8 and −353.5 kJ/mol for a single molecule in a 3.8 Å cluster of 1 and 2, respectively. The total energy diagrams exhibited a strong resemblance to the dispersion energy frameworks in both complexes. NBO charge analysis predicted the charges of the Zn(II) in complexes 1 and 2 to be 1.217 and 1.145 e, respectively. The electronic configuration of Zn1 is predicted to be [core] 4S^0.32 3d^9.98 4p^0.45 4d^0.02 5p^0.01 for 1 and [core] 4S^0.34 3d^9.97 4p^0.53 4d^0.02 for 2. The increased occupancy of the valence orbitals is attributed to the donor→acceptor interactions from the ligand groups to Zn(II). The Zn(II) complexes were examined for their cytotoxic and antimicrobial activities. Both 1 and 2 have good cytotoxic efficiency towards HCT-116 and A-549 cancerous cell lines. We found that 1 is more active (IC₅₀ = 29.53 ± 1.24 and 35.55 ± 1.69 µg/mL) than 2 (IC₅₀ = 41.25 ± 2.91 and 55.05 ± 2.87 µg/mL) against both cell lines. Also, the selectivity indices for the Zn(II) complexes are higher than one, indicating their suitability for use as anticancer agents. In addition, both complexes have broad-spectrum antimicrobial activity (IC₅₀ = 78–625 μg/mL) where the best result is found for 2 against P. vulgaris (IC₅₀ = 78 μg/mL). Its antibacterial activity is found to be good compared to gentamycin (5 μg/mL) as a positive control against this microbe. Full article

(This article belongs to the Section Coordination Chemistry)

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