Novel thiosemicarbazone complexes as single coordinated precursors for noble metal modified nickel oxide nanophotocatalysts

This study focuses on the synthesis of azo‐thiosemicarbazone ligand, which is designed by reacting 2‐hydroxy‐5‐(phenyldiazenyl)benzaldehyde with hydrazine carbothioamide. Hence, this ligand was exploited for chelation with nickel and cupric salts in (1 M:1 L) molar ratio. These synthetics were structurally investigated using a variety of physical, analytical, and spectroscopic (1D/2D‐NMR, UV–Vis, FT‐IR, and E‐mass) tools as well as theoretically. The finding demonstrated that the resulting azo‐thiosemicarbazone (H4Azo‐TSC) bonded with the nickel and cupric ions as mono/di‐basic tridentate chelators, binding them via deprotonated phenolic oxygen, imino nitrogen, and thionic/thiol sulfur atoms adopting square planar geometry. The theoretical investigation was examined by DFT/B3LYP/LanL2dZ, including energetic parameters, HOMO‐LUMO energy gap, dipole moment, and geometrical optimization, which were applied to support the complexes' geometrical structure. The in vitro microbicidal activities of the azo‐thiosemicarbazone, compared with its Ni2+ and Cu2+ complexes, display superior activity over the metal complexes against different bacterial and fungal species. The anticancer efficacy of the synthetics was tested against human lung fibroblast (WI38) and mammary gland breast cancer (MCF‐7) compared with Doxorubicin as a standard drug. The cytotoxic efficiency of metallic complexes exceeded that of un‐chelated azo‐thiosemicarbazone. The most effective complex is Ni2+ complex with IC50 equal to 11.75 and 14.05 μg/ml, respectively. It has been demonstrated that Ni2+ and Cu2+ complexes are more biocompatible than free azo‐thiosemicarbazone; this finding may be related to the chelation process.

Section: Resultsmentioning

confidence: 99%

Section: Ft-ir Spectramentioning

confidence: 99%

Section: Ft-ir Spectramentioning

confidence: 99%

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Synthesis, structural characterization, density functional theory, anticancer, and antimicrobic studies of Ni²⁺ and Cu²⁺ complexes encompassing tridentate ONS‐donor azo‐thiosemicarbazone

Hassan,

Ebrahium,

Al‐Hakimi

2024

“…Among numerous metal oxide NPs preparation methods, the thermal decomposition of single molecular precursor is of great potential 6 . This approach has received significant interest compared with multi‐step and multi‐reactants systems.…”

Section: Introductionmentioning

confidence: 99%

“…Among numerous metal oxide NPs preparation methods, the thermal decomposition of single molecular precursor is of great potential. 6 This approach has received significant interest compared with multi-step and multi-reactants systems. The main advantages of using single molecular precursor over the other conventional approaches are simplicity, elimination of further purification steps, and definite final decomposition products.…”

mentioning

confidence: 99%

Solid state conversion of novel coordinated precursors to visible light active photocatalysts with enhanced photocatalytic activity

Hasan,

Ali,

Madkour

2023

Self Cite

The new polydentate N'1,N'3‐bis((E)‐3‐oxopentan‐2‐ylidene)malonohidrazide chelating agent (H2L) and its coordinated complexes of Co2+, Cu2+, and Ni2+ were prepared and characterized by elemental analysis, molar conductance, and spectra (Fourier transform infrared [FT‐IR], ultraviolet–visible spectroscopy [UV–vis], and Fast‐Atom Bombardment Mass Spectrometry (FAB‐MS). Also, thermal and magnetic investigations were conducted. X‐ray single crystal of the H2L ligand revealed a triclinic structure with space group P‐1. In this study, we provide a one‐pot preparation approach for transition metal oxide nanoparticles (NPs) such as CuO, Co3O4, and NiO NPs. The methodology entails the thermal decomposition of coordinated metal precursors in a solid‐state environment, obviating the necessity for agitation and rinsing. The remarkable significance of this method lies in its ability to produce highly pure NPs without the requirement of washing, and it allows for systematic and efficient production. Herein, we propose a large‐scale, environmentally benign and renewable, transition metals oxide NPs such as CuO, Co3O4, and NiO using solid‐state thermal degradation of their coordinated precursors. The NPs are subjected to analysis employing a range of techniques, such as X‐ray powder diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), N2 sorpometry (BET), and UV–vis). The photocatalytic activities of the synthesized NPs were assessed using photodegradation of organic contaminants in wastewater.

A novel binuclear Zn²⁺ and Cd²⁺ complexes of carbothiohydrazide chelating agent for the corrosion protection of carbon steel alloy in 15% HCl solution

El‐Sawaf,

Madkour,

Nassar

et al. 2024

Equimolar reactions of Zn2+ and Cd2+acetates with the carbothiohydrazide, [2‐HO‐C6H4‐C(H) = N‐N(H)‐C(=S)‐N(C2H4)2O] chelating agent (H2L) have produced the binuclear [M(L)]2 metal chelates. The isolated compounds have been evaluated by elemental analyses, XRD, molar conductivities, 1H and 13C‐NMR, FTIR, FAB‐MS, UV–Vis, and thermal analyses. The crystal structure of the chelating agent has been resolved and indicates the presence of the chelating agent exclusively in its E conformer regarding the C(H) = N bond. Elemental analyses and molar conductance data indicated that the investigated metal chelates are nonelectrolytes and were formed with 2 M:2 L stoichiometry. FT‐IR along 1H‐NMR spectral data gave evidence for a di‐anionic chelating agent that bonded with central metal ions via azomethine N, deprotonated phenolic O, and thiolate S atoms. The anti‐corrosion performance of the chelating agent and its metal chelates have been evaluated for protecting carbon steel (CS) in 15% HCl aqueous solution using electrochemical examination (EIS and PDP), surface examination (SEM and XPS) and theoretical approach (DFT calculations and MC simulation). The results revealed that [Zn(L)]2 complexes remarkably performed with an inhibition efficiency of about 94.7%, which was better than those for [Cd(L)]2 complex (93.0%) and H2L (88.2%), respectively. The EIS results revealed the gradual rise of charge transfer resistance (Rct) with concentration, while the PDP proved the mixed‐type inhibition performance with cathodic advantage consistent with the Langmuir adsorption model. It was verified that the Zn (II) complex could adsorb on the metallic surface, forming a protective layer responsible for mitigating the corrosion reaction and ions diffusion. This study provided novel inhibitors with structures designed and developed for inhibiting the corrosion process with marked performance. The results derived from various methodologies contribute to a substantiated interpretation of the mechanism of inhibition.