Synthesis, characterization, and DFT study of novel metallo phtalocyanines with four carboranyl clusters as photosensitisers for the photodynamic therapy of breast cancer cells.

The synthesis and characterization of novel Zn(II) and Co(II) phthalocyanines 4 and 5, respectively containing four o-carboranyl units (40 boron atoms, 32.5% boron by weight) at the peripheral positions are described. The phthalocyanines (Pcs) were synthesized by cyclotetramerization of the previously prepared precursor 4­(2­thiol­o­carboranyl)thiolato­phthalonitrile 3 with the presence of metal salt in boiling dry DMF under a dry nitrogen atmosphere. They were characterized by elemental analysis, UV-Vis, FT-IR, MALDI-TOF mass and 1H NMR spectrometry. To elucidate the structural, spectroscopic and bonding properties of the obtained compounds, calculations with DFT/TD-DFT(Density Functional Theory/Time Dependent-Density Functional Theory) were performed. The cytotoxic effects of 4 and 5 on cancer cells and epithelial cells were determined. The targeted cytotoxicities of both compounds against cancer cells were analyzed with the cell viability test. Although, 4 caused less PDT (Photodynamic therapy) based decrease in cell viability of cancer cell line in comparison to 5, it showed comparatively high cytotoxicity against cancer cells but not epithelial cells. The IC50 (half maximal inhibitory concentration) values indicate that 4 with PDT shows 17.3 fold more cytotoxicity to breast cancer cells than epithelial cells. The selectivity in cytotoxicity of 4 makes it a good candidate for cancer treatment. Interestingly, 5 was found to be highly cytotoxic for both cancer and epithelial cell lines. Considerably, 5 might be used as a cancer drug when combined with targeting agents such as antibodies and aptamers.

Computational studies of metal carbonyl complexes of 3[4-ethyl(phenly)imino][indoline-2-one] and 3[4-butyl(phenly)imino][indoline-2-one].

Use and application of Schiff bases are extended to many different fields of technology. (ISE)M(CO)5 complex [M = Cr (1), Mo (2), W (3), and where ISE is 3[4-ethyl(phenly)imino][indoline-2-one]; and (ISB)M(CO)5 [M = Cr (4), Mo (5), W (6)], where ISB is 3[4-butly(phenly)imino][indoline-2-one] were investigated by computational methods. Computations were carried out using density functional theory (DFT) with B3LYP and CAM-B3LYP functionals, in conjunction with LanL2DZ basis set for metals and cc-PVTZ basis set for other atoms. Time-dependent density functional theory (TDDFT) was used at the same level to obtain the electronic transitions. Molecular orbital energies, UV-Vis spectra, and total electron densities of investigated molecules were shown in the gas phase and in THF. Metal complexes showed higher absorption coefficients compared to ISE and ISB in the visible region. Additionally, they displayed absorption peaks at longer wavelengths and full MLCT character in solution, and W complexes required less energy compared to the complexes of other investigated metal ions. Among the investigated systems, (ISE)W(CO)5 and (ISB)W(CO)5 complexes with lowest HOMO-LUMO gaps are found to be the best candidates for photosensitive material production. Graphical Abstract UV-Vis absorption spectra of ISE and (ISE)W(CO)5.

A new approach in biomimetic synthesis of calcium phosphate coatings using lactic acid-Na lactate buffered body fluid solution.

The main objective of this study was to investigate calcium phosphate (CaP) coatings on Ti6Al4V substrates by using the biomimetic technique. To this purpose, a new solution was developed to coat CaP on Ti6Al4V alloy substrates. The newly formulated body fluid (Lac-SBF) contained appropriate amounts of sodium lactate (NaL) and lactic acid (HL), as well as all the other ionic constituents of the human blood plasma. The inorganic ion concentrations of the Lac-SBF solutions were identical with those of human blood plasma. The new Lac-SBF solution of this study eliminated the need for using Tris/HCl or Hepes/NaOH buffers. Prior to coating, Ti6Al4V substrates were chemically treated in NaOH and/or NaOH+H(2)O(2) solutions as an alternative route and then heated at 600 degrees C for 1h in air. In the previous applications, the Cl(-) ion concentration was found to be higher than blood plasma 103mM, which exists in human blood plasma as a result of Tris/HCl which are used to prevent precipitation and to keep the pH level at certain values. In this study, instead of using Tris/HCl, HL/NaL which are generated by human body and do not show any toxic behavior, are used and Cl(-) concentration was kept at 103mM value for the first time. The prepared Lac-SBF was shown to have similar concentration to human blood plasma in terms of all inorganic ions for the first time. Solution properties were evaluated by using turbidimeter, pH meter and rheometer. The coatings were characterized using Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), and a scratch tester. The obtained results are presented and discussed.