Selective Hydrolysis of Ovalbumin by Zr-Based Lacunary Polyoxotungstate in Surfactant Solutions.

This study aims to design an artificial metalloprotease based on a Zr-containing polyoxometalate Na8[Zr(W5O18)2] [Zr(W5)2] for the hydrolysis of ovalbumin (OVA) in the presence of different surfactants, which can be used in many areas of the biological and medical sciences, particularly for targeted proteolytic drug design. For this reason, parameters, including the free energy of binding, the chemical nature of amino acid residues, secondary structures, and electrostatic potentials, of Zr(W5)2-OVA and Zr(W5)2-OVA-surfactant were analyzed by molecular docking simulations. The investigations showed that the presence of surfactants decreases the binding affinity of Zr(W5)2 for OVA amino acids, and hydrogen bonds and van der Waals interactions are formed between Zr(W5)2 and OVA amino acids. Additionally, GROMACS further illustrated the significance of SDS and CTAB surfactants in influencing the conformational changes of the OVA that lead to selective protein hydrolysis. In agreement with molecular dynamics simulation results, the experimental analysis showed more protein hydrolysis for the Zr(W5)2-OVA-surfactant systems. For instance, circular dichroism spectroscopy indicated that Zr(W5)2-OVA-CTAB and Zr(W5)2-OVA-TX-100 were more hydrolytically efficient due to the increased level of ß-structures rather than α-chains, which showed that surfactants can facilitate the accessibility of Zr(W5)2 to the cleavage sites by inducing partial unfolding of the OVA structure.

Single-molecule magnets within polyoxometalate-based frameworks.

As an extension of our interest in polyoxometalates (POMs) and lanthanoids, we report the design and synthesis of two polyoxometalate-based frameworks under hydrothermal conditions; [Ho4(PDA)4(H2O)11][(SiO4)@W12O36]·8H2O (1) and [Tb4(PDA)4(H2O)12][(SiO4)@W12O36]·4H2O (2) (H2PDA = 1,10-phenanthroline-2,9-dicarboxylic acid). Both hybrids have been characterized by elemental analysis, Fourier transform infrared spectroscopy, thermogravimetric analysis, and powder/single-crystal X-ray diffraction. According to the structural analysis, 1 and 2 consist of 2D-cationic coordination polymers based on the respective lanthanoids and PDA2- as well as Keggin anions that reside in the interspaces between two adjacent layers as discrete counterions connected by extensive hydrogen bonding. Although the overall structures of 1 and 2 are composed of cationic and anionic layers, there are many differences in the cationic layers such as various coordination modes of PDA2-, different void shapes, and the existence of dinuclear Tb(III) units only in 2. Frameworks 1 and 2 were further characterized by dc and ac magnetic measurements and both exhibit slow relaxation of magnetization at low temperatures under an applied dc field. Their single-molecule magnet (SMM) properties are investigated, where weak field-induced SMM behaviour is observed at low temperatures in dynamic magnetic studies.