The interaction of sodium phytate hydrate C6H18O24P6·xNa·yH2O (phytNa) with Cu(OAc)2·H2O and 1,10-phenanthroline (phen) led to the anionic tetranuclear complex [Cu4(H2O)4(phen)4(phyt)]·2Na+·2NH4+·32H2O (1), the structure of the latter was determined by X-ray diffraction analysis. The phytate 1 is completely deprotonated; six phosphate− fragments (with atoms P1–P6) are characterized by different spatial arrangements relative to the cyclohexane ring (1a5e conformation), which determines two different types of coordination to the complexing agents—P1 and P3, P4, and P6 have monodentate, while P2 and P5 are bidentately bound to Cu2+ cations. The molecular structure of the anion complex is stabilized by a set of strong intramolecular hydrogen bonds involving coordinated water molecules. Aromatic systems of phen ligands chelating copper ions participate in strong intramolecular and intermolecular π-π interactions, further contributing to their association. At the supramolecular level, endless stacks are formed, in the voids of which sodium and ammonium cations and water molecules are present. The stability of 1 in the presence of human serum albumin (HSA) was investigated using Electron Paramagnetic Resonance (EPR) spectroscopy. Continuous wave (CW) EPR spectra in water/glycerol frozen solution clearly indicate a presence of an exchange-coupled Cu(II)-Cu(II) dimeric unit, as well as a Cu(II) monomer-like signal arising from spins sufficiently distant from each other, with comparable contributions of two types of signals. In the presence of albumin at a 1:1 ratio (1 to albumin), the EPR spectrum changes significantly, primarily due to the reduced contribution of the S = 1 fraction showing dipole–dipole splitting. The biological activity of 1 in vitro against the non-pathogenic (model for Mycobacterium tuberculosis) strain of Mycolicibacterium smegmatis is comparable to the first-line drug for tuberculosis treatment, rifampicin.
The creation of the “correct” surface in heterogeneous catalysis is an important condition for the optimal operation of a number of catalytic systems, for example, hydrogenation (nitrobenzene dicyclopentadiene).
Silver complexes are potential antimicrobial agents that trigger destructive processes in bacterial cells, leading to their death. Their ability to simultaneously stimulate tissue regenerative properties also makes them promising components in the development of medical materials. A common complication arising from the treatment of bone tissue damage is hospital-acquired infection, requiring repeated revision surgeries. The use of bone grafts with antibacterial properties can help solve this problem. New pyridine complexes of silver(I) with thiophenecarboxylic (Htph) and nitric acid anions have been synthesized: [Ag(tph)(py)2]n·nHtph (1, py—pyridine) and [Ag(bpy)]n·nNO3 (2, bpy—4,4′-bipyridine), the structures of which have been determined using X-ray analysis. Despite the fact that 2 is a known structure, we were able to obtain new cell parameters by conducting an X-ray diffraction analysis at a lower temperature of 100 K. According to X-ray diffraction data, both compounds are polymers in which the cationic part is formed by linear fragments (CNAg = 2) [Ag(py)2]+ (1)/[Ag(bpy)2]+ (2), and acid anions act as counterions. The presence of intermolecular and non-valent π-π interactions provides additional stabilization of supramolecular levels. Aqueous solutions 1 and 2 are stable for two weeks, according to UV-Vis data. Incubation of crosslinked resorbable polymer matrices functionalized separately with complex 1 or 2 in saline solution revealed a sustained, prolonged release of silver ions over 14 days. Evaluation of the antimicrobial potential of 1 and 2 against Gram-positive/Gram-negative species and fungi demonstrated moderate, controlled bacteriostatic growth inhibition broadly across tested strains, confirming the bifunctionality of the crosslinked hybrid matrix systems—moderate suppression of bacterial growth while simultaneously stimulating tissue regeneration. An increase in cell viability, expressed in their active proliferation under the influence of complexes 1 and 2 up to 156%, as well as calcium deposition, indicates the high cytocompatibility and pro-mineralization capacity of the new compounds.
Drugs and drug candidate compounds commonly suffer from poor solubility and permeability. One promising strategy to mediate these drawbacks is use of novel solvents, such as deep eutectic compositions. The present research aims to determine the applicability of this approach for therapeutic metal complexes on the example of [Cu(Fur)2(Phen)] (Fur = furoate-anion, Phen = 1,10-phenantroline) and [Cu(Fur)2(Neoc)(H2O)] (Fur = furoate-anion, Neoc = 2,9-dimetyl-1,10-phenanthroline) with molar weight of appx. 500 Da. Interaction of the metal complexes with the deep eutectic solvent (DES) reline was studied using electron paramagnetic resonance (EPR). Minimal inhibitory concentrations of the complexes dissolved in DES and dimethyl sulfoxide (DMSO) were determined and found to be equivalent in both solvents. That is, use of reline as a solvent did not alter the functional properties of the metal complexes. Changes in the transdermal permeation of the complexes in DMSO and DES were assessed using a Franz diffusion cell. It was discovered that depending on the structure of the complex, the permeability might either increase (from 15 to 30%) or decrease (from 13 to 8%) with changes in the solvent, and this can be used to develop dosing strategies. Therapeutic eutectogels were successfully produced by impregnating SiO2 nanoparticles with the metal complex solution in DES, facilitating convenient topical application.