The interaction of human serum albumin (HSA) with amphiphilic block copolymer Pluronic F127 has been investigated by several physical methods. Interest in studying this system stems from a broad range of bioactivities involving both macromolecules. Serum albumins constitute a significant class of proteins in the circulatory system, acting as carriers for a wide spectrum of compounds or assemblies. Pluronic block copolymers have revealed their capacity to ferry a variety of biologically active compounds. Circular dichroism, rheological measurements, and differential scanning microcalorimetry (μDSC) were employed to get insight into the interaction betweeen the two macromolecules. The results reveal that Pluronic F127 induces conformational changes to albumin if it is organized in a micellar form, while albumin influences the self-assembly of Pluronic F127 into micelles or gels. F127 micelles, however, induce smaller conformational changes compared to ionic surfactants. The μDSC thermograms obtained for HSA and/or F127 show that HSA shifts the critical micellar temperature (cmt) to lower values, while concurrently the HSA denaturation behavior is influenced by F127, depending on its concentration. Rheological measurements on solutions of F127 17% have shown that a sol-to-gel transition occurs at higher temperatures in the presence of HSA and the resulting gel is weaker. The global profile on HSA/F127 systems was complemented by local information provided by EPR measurements. A series of X-band EPR experiments was performed with spin probes 4-(N,N'-dimethyl-N-hexadecyl)ammonium-2,2',6,6'-tetramethylpiperidine-1-oxyl iodide (CAT16) and 5-doxyl stearic acid (5-DSA). These spin probes bind to albumin sites and are sensitive to phase transformations in Pluronic block copolymer solutions. For a given F127 concentration, the spin probe binds only to HSA below cmt and migrates to the F127 micelles above cmt. The collective data suggest soft interactions between the macromolecules, with the emerging results projecting potential applications linked to reaching optimal conditions for certain drug formulations.
The increasing microbial resistance to conventional antibiotics turned the attention to phytochemicals used traditionally to treat infected wounds. Some can modulate or modify bacterial resistance and potentiate their activity. Collagen hydrogels containing all the combinations between 5, 10 and 15% of tannic acid (TA) and 1.82, 4.55 and 9.09% chlorhexidine digluconate (CHDG), pH % 4 were prepared. FT-IR spectra showed that collagen interacts stronger with TA than with CHDG, TA interacts with CHDG at high concentrations and collagen conformation is not affected, so hydrogels can be used as valuable biomaterials. The preservation of collagen's triple-helical conformation was demonstrated also by the ultraviolet-circular dichroism (UV-CD) spectroscopy. The hydrogels revealed an overall pseudoplastic rheological behaviour, being easily destroyed under the action of shear rates higher than about 20 s À1 during rotational viscometry tests. However, all the hydrogels showed a viscoelastic behaviour with an elastic part that prevails over the viscous contribution, as shown from oscillatory rheometry results. The high viscosity at rest assures a good adherence of the hydrogels on wound, while their elasticity prevents the breakdown of the applied layer.
In this work we report our studies concerning the synthesis and characterisation of a series of imine derivatives that incorporate the 2-phenylpyridine (2-ppy) core. These derivatives were used in the cyclometalating reactions of platinum(II) or palladium(II) in order to prepare several complexes with liquid crystalline properties. Depending on the starting materials used as well as the solvents employed, different metal complexes were obtained, some of them showing both liquid crystalline behaviour and luminescence properties at room temperature. It was found that, even if there are two competing coordination sites, the cyclometalation process takes place always at the 2-ppy core with (for Pt) or without (for Pd) the imine bond cleavage. We successfully showed that it is possible to prepare emissive room temperature liquid crystalline materials based on double cyclopalladated heteroleptic complexes by varying the volume fraction of the long flexible alkyl tails on the ancillary benzoylthiourea (BTU) ligands.
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