Synthesis,Characterization, Speciation,and Biological Studies on Metal Chelates of Carbohydrates with Molecular Docking Investigation

The role of starch aerogel (St-AG) and carboxymethyl cellulose (CMC) as biolgical active compounds, when they subjected for complexation with metal ions, is assessed in this work. The complexation is carried out with palladium(II) and copper(II) ions, in solid state. Different tools of analysis are carried out to characterize and elucidate the structures of these complexes, namely: elemental analysis, IR, thermal analysis, magnetic measurement and molar conductance techniques. All synthesized complexes are formed with 1:2 (metal:ligand) stoichiometry except the case of aerogel starch 1:1 (Pd:starch). All isolated complexes show a satisfactory cytotoxic effect results against colon cancer cell lines HCT11. Additionally, these complexes are screened for their antibacterial activities against two types of Gram positive and negative bacteria. Molecular docking investigation confirmed the cytotoxicity and antibacterial results. Proton–ligands association constants and their complex formation constants with some bivalent metal ions, using potentiometric method show that the complexes formed in solution have a stoichiometry of 1:1 [metal:ligand]. The effects of metal ion, ionic radius, electronegativity and nature of ligand on the formation constants are discussed. The formation constants of the complexes with 3D transition metals followed the order Mn²⁺ < Co²⁺ < Ni²⁺ < Cu²⁺ > Zn²⁺.     

Ir(III) and Ru(II) Complexes in Photoredox Catalysis and Photodynamic Therapy: A New Paradigm towards Anticancer Applications

Individually, photoredox catalysis (PC) and photodynamic therapy (PDT) are well-established concepts that have experienced a remarkable resurgence in recent years, leading to significant progress in organic synthesis for PC and clinical approval of anticancer drugs for PDT. But, very recently, new photoredox catalyst systems based on Ir(III) and Ru(II) complexes have garnered significant interest because they can simultaneously be used as PDT agents apart from their demonstrated PC activity. This highlight discusses the unique PC behavior of emerging Ir(III)- and Ru(II)-based systems while also examining their potential PDT activity in cancer treatment.     

A comparative study on the performance of M (Rh,Ru, Ni)-promoted metallurgical waste driven catalysts for H2 production by glycerol steam reforming

A comprehensive study was conducted on the performance of M-promoted (M = 1%Ru, 1%Rh, 5%Ni) upgraded slag oxide metallurgical waste catalysts (M-UGSO) for hydrogen production by glycerol steam reforming (GSR). The results confirmed that the tendency of the incorporated metal to interact with Mg/Fe containing species within UGSO plays a key role in the surface availability of the corresponding metal, structural changes after reduction, and catalyst stability. Aside its best stability, 5% Ni-UGSO showed a performance (glycerol conversion to gaseous products of 100% and H₂ yield of 74%) comparable with 1% Rh-UGSO (100% and 78%, respectively) or even surpassing that of 1% Ru-UGSO (94% and 71%, respectively), as noble metal-based catalysts. Synergistic cooperation was achieved by incorporated metals (M) and Fe/Mg containing species within UGSO, resulting in enhanced glycerol and water activation. The weakest results of Ru-UGSO could be justified by lack of propensity for MgO–RuO₂ interaction on UGSO surface.     

Homogeneously dispersed cobalt/iron electrocatalysts with oxygen vacancies and favorable hydrophilicity for efficient oxygen evolution reaction

Rational design of highly conductive and hydrophilic electrocatalysts are extremely important to promote their oxygen evolution reaction (OER). In this work, a homogeneously dispersed carbon-based cobalt/iron catalyst (Co/Fe–C) with abundant oxygen vacancies and favorable hydrophilicity is fabricated via a facile metal-polyphenol complexes strategy. The tannic acid (TA) and fulvic acid (FA) derived 0.3 Co/Fe–C catalysts show greatly similar morphologies, as well as the performance optimization process of electrocatalytic OER. Specifically, the TA-derived 0.3 Co/Fe–C catalyst exhibits an overpotential of 284 mV at 10 mA cm^?2 for OER in alkaline electrolyte. Combined a series of characterization techniques suggest that abundant oxygen vacancies and favorable surface hydrophilicity can improve electronic conductivity of the catalyst and accelerate reactant adsorption and charge transfer rate on the catalyst surface, thus promoting OER activity of the catalysts. This study might provide a new perspective to construct advanced electrocatalysts with oxygen vacancies and hydrophilic surface for electrocatalytic applications.     

Predictive association of metal–organic systems in the solid-state: the molecular electrostatic potential based approach

Designing crystalline solids with improved properties or performances remains a challenging task, despite great strides that have been made within the field of crystal engineering since its birth several decades ago. Herein, we are bringing examples that illustrate recent successes in taking supramolecular synthetic guidelines from the organic crystal engineering and adjusting those to metal-containing systems, particularly to the lower-dimensional ones. The versatility of calculated molecular electrostatic potential (MEP) as a new crystal engineering tool is demonstrated.     

Component spectroscopic properties of light-harvesting complexes with DFT calculations

Photosynthesis is a fundamental process in biosciences and biotechnology that influences profoundly the research in other disciplines. In this paper, we focus on the characterization of fundamental components, present in pigment-protein complexes, in terms of their spectroscopic properties such as infrared spectra, nuclear magnetic resonance, as well as nuclear quadrupole resonance, which are of critical importance for many applications. Such components include chlorophylls and bacteriochlorophylls. Based on the density functional theory method, we calculate the main spectroscopic characteristics of these components for the Fenna-Matthews-Olson light-harvesting complex, analyze them and compare them with available experimental results. Future outlook is discussed in the context of current and potential applications of the presented results.     

Supramolecular Assembly on Coordination of Azopolymer Complexes: A Review

This review gives an account of the coordination chemistry of supramolecular azopolymer complexes. The syntheses and structures of azomonomers and their azopolymer complexes were described. Spectral techniques such as (IR, ¹H-NMR, ESR) and thermal analysis were investigated. Supramolecular architectures assembled were exhibited through weak interaction including hydrogen bonding and π–π stacking. The spectral data indicate geometry of azopolymer complexes and the orbital reduction factors. ESR spectral data provided information about their structures on the basis of Hamiltonian parameters and degree of covalency. All the azopolymer complexes are ESR active due to the presence of an unpaired electron. The force constant F_U–O(mdyn/Å) and the bond length R_U–O (Å) of the U–O bond were calculated from the IR data and related to the electronic properties of the substituents. Wilson's method, the matrix method, Badger's formula, and the Jones and El-Sonbati equations were used to calculate the U–O bond distances from the values of the stretching and interaction force constants. The most probable correlations between U–O force constant to U–O bond distance were satisfactorily discussed in terms of Badger's rule, and the Jones and El-Sonbati equations. The thermal stability was investigated using thermogravimetric analysis. The results showed that the azopolymer complexes are mostly more stable than the homopolymer. The stability of the proton ligand/metal ligand constants in the monomeric and polymeric forms was studied carefully using potentiometery. Based on the thermodynamic functions, the dissociation process is nonspontaneous, endothermic and entropically unfavorable. The metal complexes that were formed exhibited spontaneous, endothermic and entropically favorable behavior.     

Synthesis and Characterization of Co Nanocomposite Based on Poly(benzimidazole-amide) Matrix and Their Behavior as Catalyst in Oxidation Reaction

2,6-Bis(5-amino-1H-benzimidazol-2-yl)pyridine was prepared and characterized by Fourier transform infrared spectroscopy, elemental analysis, ¹H-NMR, and ¹³C-NMR spectroscopic methods. Then a new poly(benzimidazole-amide) was synthesized by polymerization of the corresponding diamine and isophthalic acid. The obtained poly(benzimidazole-amide) exhibited good yield and high thermal stability. Due to the existence of benzimidazole moieties in polymer’s structure, it has the tendency to form complexes with metal ions. So, a new poly(benzimidazole-amide)/Co nanocomposite was prepared. Morphological studies revealed that metal nanoparticles were dispersed in the polymer matrix without any aggregation. poly(benzimidazole-amide)/Co nanocomposite was used as a catalyst in the oxidation of ethyl benzene to acetophenone with tert-butyl hydroperoxide.