Stationary and time-resolved studies of 9,10,19,20-tetramethylporphycene and 9,10,19,20-tetra-n-propylporphycene in condensed phases reveal the coexistence of trans and cis tautomeric forms. Two cis configurations, cis-1 and cis-2, play a crucial role in understanding the excited-state deactivation and tautomer conversion dynamics. The trans-trans tautomerization, involving intramolecular transfer of two hydrogen atoms, is extremely rapid (k ≥ 10(13) s(-1)), both in the ground and lowest electronically excited states. The cis-1-trans conversion rate, even though the process is thermodynamically more favorable, is much slower and solvent-dependent. This is explained by the coupling of alkyl group rotation with the hydrogen motion. Excited-state deactivation is controlled by solvent viscosity: the S(1) depopulation rate decreases by more than 2 orders of magnitude when the chromophore is transferred from a low-viscosity solution to a polymer film. Such behavior confirms a model for excited state deactivation in porphycene, which postulates that a conical intersection exists along the single hydrogen transfer path leading from the trans to a high energy cis-2 tautomeric form. For this process, the tautomerization coordinate includes not only hydrogen translocation but also large-amplitude twisting of the two protonated pyrrole moieties attached to the opposite sides of the ethylene bridge.
Surfaces of iron oxide of ferrimagnetic magnetite (Fe3O4) nanoparticles (MNPs) prepared by Massart's method and their functionalized form (f-MNPs) with succinic acid, L-arginine, oxalic acid, citric acid, and glutamic acid were studied by dynamic light scattering (DLS), Fourier transform infrared spectroscopy (FTIR-S), UV-vis, thermogravimetric analysis (TGA)/differential scanning calorimetry (DSC), X-ray photoelectron spectroscopy (XPS), and reflection electron energy loss spectroscopy (REELS). The XPS analysis of elements and their chemical states at the surface of MNPs and f-MNPs revealed differences in chemical bonding of atoms, content of carbon–oxygen groups, iron oxide forms, iron oxide magnetic properties, adsorbed molecules, surface coverage, and overlayer thickness, whereas the Auger parameters (derived from XPS and Auger spectra) and elastic and inelastic scattering probabilities of electrons on atoms and valence band electrons (derived from REELS spectra) indicated modification of surface charge redistribution, electronic, and optical properties. These modified properties of f-MNPs influenced their biological properties. The surfaces biocompatible for L929 cells showed various cytotoxicity for HeLa cells (10.8–5.3% of cell death), the highest for MNPs functionalized with oxalic acid. The samples exhibiting the largest efficiency possessed smaller surface coverage and thickness of adsorbed molecules layers, the highest content of oxygen and carbon–oxygen functionalizing groups, the highest ratio of lattice O2− and OH− to C sp2 hybridizations on MNP surface, the highest ratio of adsorbed O− and OH− to C sp2 hybridizations on adsorbed molecule layers, the closest electronic and optical properties to Fe3O4, and the lowest degree of admolecule polymerization. This high cytotoxicity was attributed to interaction of cells with a surface, where increased content of oxygen groups, adsorbed O−, and OH− may play the role of additional adsorption and catalytic sites and a large content of adsorbed molecule layers of carboxylic groups facilitating Fenton reaction kinetics leading to cell damage.
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