The rich crystal chemistry of mullite-type Bi 2 M 4 O 9 (M = Fe, Al, Ga) offers multiple potential applications. In particular, the strong absorption of visible light shown by Bi 2 Fe 4 O 9 has led to an influx of research on its photocatalytic properties. However, most of the published studies involve the decolorization of dyes and take it as proof of its photocatalytic activity; furthermore, there are no reports on its conduction and valence band edges, and, thus, the actual redox characteristics of the photogenerated charge carriers have not been determined. Here, we evaluate the photocatalytic activity toward methanol oxidation under monochromatic visible light (λ = 450 nm) irradiation of 12 different members of the Bi 2 (Al 1−x Fe x ) 4 O 9 (x = 0−1) series of compounds. The reaction rate reaches its highest value at an iron fraction of x = 0.1, while the compounds with the highest iron fractions present negligible activity. Based on an extensive characterization, which included the Rietveld refinement of the XRD patterns, the measurement of the specific surface areas by the BET method, and the determination of the flat-band potentials by the Mott−Schottky method, we rationalize the results on the basis of two opposing factors: the incorporation of iron narrows the fundamental bandgap and thus improves light capture, but at the same time it lowers the conduction band edge, hindering the oxygen reduction half-reaction and thus promoting electron−hole recombination. Our work highlights the importance of a proper band edge engineering for photocatalytic applications and underlines the inadequacy of dye decolorization tests for visible-light-active materials.
The main goal of this work was to report the synthesis, characterization, and cytotoxicity study of a novel copper(II)-sunitinib complex, CuSun. It has been synthesized and characterized in solid state and in solution by different methods (such as DFT, FTIR, Raman, UV-vis, EPR, NMR, etc.). The solid-state molecular structure of trichlorosunitinibcopper(II), where sunitinib: N-[2-(diethylamino)ethyl]-5-[(Z)-(5-fluoro-2-oxo-1H-indol-3-ylidene)methyl]-2,4-dimethyl-1H-pyrrole-3-carboxamide, for short Cu(Sun)Cl3, was determined by X-ray diffraction. It crystallizes in the triclinic space group P-1 with a = 7.9061(5) Å, b = 12.412(1) Å, c = 13.7005(8) Å, α = 105.021(6)°, β = 106.744(5)°, γ = 91.749(5)°, and Z = 2 molecules per unit cell. Also, we have found π-π interactions and classic and non-classic H-bonds in the crystal structure by using Hirshfeld surface analysis. In the speciation studies, the complex has dissociated in protonated sunitinib and chlorocomplex of copper(II), according to 1HNMR, EPR, UV-vis and conductimetric analysis. Molecular docking of the complex in both, ATP binding site and allosteric site of VEGFR2 have shown no improvement in comparison to the free ligand. Besides, cytotoxicity assay on HepG2 cell line shows similar activity for complex and ligand in the range between 1–25 μM supporting the data obtained from studies in solution.
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