Over the last decade, therapeutic metallodrugs have become substantially effective in the treatment of cancer. Thus, developing new effective anticancer drugs is a significant research area against the continuing increase in cancers worldwide. In the search for heterobimetallic prodrugs containing V/Cu, a new cyclo-tetravanadate was synthesized and characterized by UV-visible and FTIR spectroscopies and single-crystal X-ray diffraction. L-Glutamine and 1,10-phenanthroline allow the crystallization of [Cu(L-Gln)(phen)(H₂O)]₄[V₄O₁₂]∙8(H₂O) (1), in which the cyclo-tetravanadate acts as a free anion. Density functional theory (DFT) calculations were carried out to characterize the frontier molecular orbitals and molecular electrostatic potential. Global reactivity indexes were calculated and analyzed to give insight into the cyclo-tetravanadate anion and complex counterions interactions. Also, using Bader’s theory of atoms in molecules (AIM), non-covalent interactions were analyzed. Docking analysis with the Casiopeina-like complex resulting from the hydrolysis of compound 1 provided insights into these complex potential anticancer activities by interacting with DNA/tRNA via H-bonds and hydrophobic interactions. The release of both components could act together or separately, acting as prodrugs with potential dual antineoplastic activities.

The antidiarrheal properties of 19-deoxyicetexone, a diterpenoid isolated from Salvia ballotiflora were evaluated on castor oil-, arachidonic acid (AA)- and prostaglandin (PGE₂)-induced diarrhea in rodent models. The structure of 19-deoxyicetexone was determined by X-ray crystallography, mass spectrometry (EI-MS), as well as ultraviolet (UV-Vis), infrared (FT-IR) and nuclear magnetic resonance (NMR) spectroscopies. This compound significantly and dose-dependently reduced frequency of stooling in castor oil-induced diarrhea, and at dose of 25 mg/kg it also inhibited diarrhea induced with AA, while it had no effect on PGE₂-induced diarrhea. This compound at doses of 25 mg/kg also diminished castor oil-induced enteropooling and intestinal motility, and inhibited the contraction of the rats’ ileum induced by carbachol chloride at a concentration of 100 µg/mL. 19-Deoxyicetexone did not present acute toxicity at doses of 625 mg/kg. Its antidiarrheal activity may be due to increased reabsorption of NaCl and water and inhibition of the release of prostaglandins, gastrointestinal motility and fluid accumulation in the intestinal tracts of rats. These findings suggest that 19-deoxyicetexone may be used in the treatment of diarrhea, although more studies must be carried out to confirm this.

Cancer represents a major worldwide public health problem. While significant advances in different fronts are being made to combat the disease, the development of new metal-based drugs with cytotoxic capabilities is of high relevance. This work presents a heterobimetallic molecule comprising two moieties with a structure similar to Casiopeina II-gly. One of them has a cyclotetravanadate anion that functions as an inorganic bridge coordinating two Cu (II) atoms resulting in a hexanuclear [Cu(phen)(Gly)-µ2-V₄O₁₂-Cu(phen)(Gly)]²⁻ complex, which is counterbalanced by two isolated [Cu(phen)(Gly)(H₂O)]¹⁺ cations. Ten water molecules arranged in two sets of five-member chains also play an essential role in the 3D supramolecular structure of the compound. The molecule was designed to provide Cu and V, two metals with proven anticancer capabilities in the same molecular structure. The compound was synthesized and characterized by elemental analysis; visible, FTIR, and Raman spectroscopies; ⁵¹V Nuclear Magnetic Resonance; cyclic voltammetry; and monocrystalline X-ray diffraction. The structural, spectroscopic, and electronic properties of the compound were calculated through the density functional theory (DFT) using the Minnesota functional M06-2X and the Def2TZVP/LANL2TZ(f) basis sets with an effective core potential (ECP) for metals. Noncovalent interactions were analyzed using a natural population analysis (NPA) and Hirshfeld surfaces. The compound upon dissociation provides two metals that can interact with important biological targets in a variety of cancer cell models.

In this work, we report the electrochemical response of a family of Co(II) complexes, [Co^II(L)₃]²⁺ and [Co^II(L’)₂]²⁺ (L = 2,2’-bipyridine, 1,10-phenanthroline, 3,4,7,8-tetramethyl-1,10-phenanthroline, 5,6-dimethyl-1,10-phenanthroline, and 4,7-diphenyl-1,10-phenanthroline; L’ = terpyridine and 4-chloro-terpyridine), in the presence and absence of CO₂ in order to understand the role of the redox potential and molecular structure on the molecular catalysis of CO₂ reduction. The tris chelate complexes exhibited three electron transfer processes [Co^II(L)₃]²⁺ ⇄ [Co^III(L)₃]³⁺ + 1e⁻, [Co^ΙΙ(L)₃]²⁺+1e⁻ ⇄ [Co^Ι(L)₃]⁺, and [Co^Ι(L)₃]⁺ + 2e^- ⇄ [Co^Ι(L)(L⁻)₂]⁻. In the case of complexes with 1,10-phen and 2,2-bipy, the third redox process showed a coupled chemical reaction [Co^Ι(L)(L⁻)₂]⁻ → [Co^Ι(L⁻)₂]⁻ + L. For bis chelate complexes, three electron transfer processes associated with the redox couples [Co^ΙΙ(L)₂]/[Co^III(L)₂]³⁺, [Co^ΙΙ(L)₂]²⁺/[Co^Ι(L)₂]⁺, and [Co^Ι(L)₂]⁺/[Co^Ι(L)(L⁻)] were registered, including a coupled chemical reaction only for the complex containing the ligand 4-chloro-terpyridine. Foot to the wave analysis (FOWA) obtained from cyclic voltammetry experiments allowed us to calculate the catalytic rate constant (k) for the molecular catalysis of CO₂ reduction. The complex [Co(3,4,7,8-tm-1,10-phen)₃]²⁺ presented a high k value; moreover, the complex [Co(4-Cl-terpy)₃]²⁺ did not show catalytic activity, indicating that the more negative redox potential and the absence of the coupled chemical reaction increased the molecular catalysis. Density functional theory (DFT) calculations for compounds and CO₂ were obtained to rationalize the effect of electronic structure on the catalytic rate constant (k) of CO₂ reduction.

Citrulline is a non-protein amino acid that acts as a metabolic intermediate in the urea cycle and arginine synthesis. It is present in some foods, although its name derives from watermelon (Citrullus vulgaris), from which it was first identified. Under normal conditions, Citrulline exists as a zwitterion in aqueous solutions since its carboxylic and amine groups can act as Lewis donors to chelate metal cations. In addition, Citrulline possesses in the aliphatic chain a terminal ureide group, which could also coordinate. Although Citrulline is comparable to other classical amino acids, its coordination chemistry has yet to be explored. Only two metal complexes have been reported, and the copper complex is a polymeric and insoluble material. As part of our search for active Casiopeina^® analogs, we created a more soluble complex by combining 2,2′-Bipyridine into a new mixed material, resulting in the mononuclear complex [Cu(Bipy)(Citr)(H₂O)(NO₃)]·H₂O. Single-crystal X-ray diffraction, spectroscopic methods (FT-IR, UV-Vis, Raman), and mass spectrometry characterized the material. Interestingly, both isomers of Citrulline, R(D), and S(L) are present in the same crystal. In addition, the molecular structure and electronic properties of the complex were calculated using density functional theory (DFT). Non-covalent interactions were characterized using the atoms-in-molecules (AIM) approach and Hirshfeld surface (HS) analysis. This ternary complex containing Citrulline and 2,2′-Bipyridine will be used for docking calculations and preliminary biological studies using calf thymus DNA (CT-DNA) and plasmid pUC19 as a first approximation to cytotoxic activity against cancer cell lines.

Citrulline (C₆H₁₃N₃O₃) is an amino acid found in the body as a zwitterion. This means its carboxylic and amine groups can act as Lewis donors to chelate metal cations. In addition, citrulline possesses a terminal ureido group on its aliphatic chain, which also appears to coordinate. Here, two new mixed complexes of citrulline were made with 1,10-phenanthroline and 2,2′-bipyridine. These compounds, once dissolved in water, gave aquo-complexes that were subject to DFT studies and in vitro toxicity studies on cancer cell lines (HeLa, MDA-MB-231, HCT 15, and MCF7) showed promising results. Docking studies with DNA were also conducted, indicating potential anticancer properties.