fac-{Ru(CO)(3)}(2+)-core complexes and design of metal-based drugs. Synthesis, structure, and reactivity of Ru-thiazole derivative with serum proteins and absorption-release studies with acryloyl and silica hydrogels as carriers in physiological media

Cini, R., Defazio, S., Tamasi, G., Casolaro, M., Messori, L., Casini, A., Morpurgo, M. and Hursthouse, M. (2007) fac-{Ru(CO)(3)}(2+)-core complexes and design of metal-based drugs. Synthesis, structure, and reactivity of Ru-thiazole derivative with serum proteins and absorption-release studies with acryloyl and silica hydrogels as carriers in physiological media. Inorganic Chemistry, 46 (1), 79-92. (doi:10.1021/ic060755s).

Abstract

The reaction of [Ru-2(CO)(6)Cl-4], 1, with excess THZ (1,3-thiazole) in absolute ethanol at 55 degrees C produces fac-[Ru(CO)(3)Cl-2(THZ)], 2, in high yield. [Ru(CO)(2)Cl-2(THZ)(2)], 3, is formed at higher temperature (ca 70 degrees C) and higher concentration of THZ. The X-ray structures of the new compounds have been determined, and density functional studies performed at the hybrid B3LYP/(Lanl2DZ, Ru; 6-311+G**, CHClNOS) level allowed the estimation of the structures of several conformers as well as that of their relative total electronic energies. Compound 2 is soluble (slowly) in aqueous media, where it reacts with the transport proteins bovine serum albumin (BSA) and human apotransferrin (HTF), and at a lower extent with calf thymus DNA (CT-DNA) and with guanosine-5'-monophosphate (GMP). The complex molecule is adsorbed by certain synthetic acryloyl polymers that have terminal carboxylate functions and is embedded in silica gels when these latter are prepared in the presence of a solution of 2. Ruthenium species are slowly released from the loaded gels into physiological solutions at pH 7.4. The reactivity of 2 with biomolecules and synthetic hydrogels makes it a compound of interest for anticancer and antimetastases tests.

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