Nowadays, luminescent materials attract wide attention due to their valuable characteristics and broad area of potential application. Luminescent silicone-based polymers possess unique properties, such as flexibility, hydrophobicity, thermal and chemical stabilities, etc., which allow them to be utilized in various fields, such as optoelectronics, solid-state lasers, luminescent solar concentrators, sensors, and others. In the present work, a metal-ligand interaction approach was applied to obtain new cross-linked luminescent polymers based on multiligand polysiloxanes with grafted β-diketone fragments and organoeuropiumsiloxanes containing various organic substituents. Organoeuropiumsiloxanes were utilized as a source of Eu3+ ions due to their compatibility with the silicon matrix. All synthesized polymers were fully characterized and their physicochemical, mechanical, self-healing, optical, and thermal properties were studied.
Carotenoids are potent antioxidants with a wide range of biomedical applications. However, their delivery into human cells is challenging and relatively inefficient. While the use of natural water-soluble carotenoproteins capable to reversibly bind carotenoids and transfer them into membranes is promising, the quantitative estimation of the delivery remains unclear. In the present work, we studied echinenone (ECN) delivery by cyanobacterial carotenoprotein AnaCTDH (C-terminal domain homolog of the Orange Carotenoid Protein from Anabaena), into liposome membranes labelled with BODIPY fluorescent probe. We observed that addition of AnaCTDH-ECN to liposomes led to the significant changes in the fast-kinetic component of the fluorescence decay curve, pointing on the dipole-dipole interactions between the probe and ECN within the membrane. It may serve as an indirect evidence of ECN delivery into membrane. To study the delivery in detail, we carried out molecular dynamics modeling of the localization of ECN within the lipid bilayer and calculate its orientation factor. Next, we exploited FRET to assess concentration of ECN delivered by AnaCTDH. Finally, we used time-resolved fluorescence anisotropy to assess changes in microviscosity of liposomal membranes. Incorporation of liposomes with β-carotene increased membrane microviscosity while the effect of astaxanthin and its mono- and diester forms was less pronounced. At temperatures below 30 °C addition of AnaCTDH-ECN increased membrane microviscosity in a concentration-dependent manner, supporting the protein-mediated carotenoid delivery mechanism. Combining all data, we propose FRET-based analysis and assessment of membrane microviscosity as potent approaches to characterize the efficiency of carotenoids delivery into membranes.
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