Synthesis, Characterization, Fluorescence Properties, and DFT Modeling of Difluoroboron Biindolediketonates.

We report a simple and efficient strategy to enhance the fluorescence of biocompatible biindole diketonates (bdks) in the visible spectrum through difluoroboronation (BF2bdks complexes). Emission spectroscopy testifies an increase in the fluorescence quantum yields from a few percent to as much as >0.7. This massive increment is essentially independent of substitutions at the indole (-H, -Cl, and -OCH3) and corresponds to a significant stabilization of the excited state with respect to non-radiative decay mechanisms: the non-radiative decay rates are reduced by as much as an order of magnitude, from 109 s-1 to 108 s-1, upon difluoroboronation. The stabilization of the excited state is large enough to enable sizeable 1O2 photosensitized production. Different time-dependent (TD) density functional theory (DFT) methods were assessed in their ability to model the electronic properties of the compounds, with TD-B3LYP-D3 providing the most accurate excitation energies. The calculations associate the first active optical transition in both the bdks and BF2bdks electronic spectra to the S0 → S1 transition, corresponding to a shift in the electronic density from the indoles to the oxygens or the O-BF2-O unit, respectively.

Synthesis of a new sulfonated-hexachlorobiphenyl standard for environmental analysis, ecotoxicological, and toxicological studies.

Sulfonated-polychlorinated biphenyls (sulfonated-PCBs) are a newly discovered class of PCB metabolites. They were observed for the first time in polar bear serum and lately, in soil, together with hydroxy-sulfonated-PCBs. Their presence is ubiquitous in soils, and their estimated physical chemical properties show high mobility in water, compared to the parent compounds. However, no single pure standards exist so far and therefore their quantification in the environmental matrices is not accurate. Additionally, pure standards are needed to experimentally determine their physical chemical properties, as well as the ecotoxicological and toxicological characteristics. In the present work, the challenging goal of preparing a polychlorinated biphenyl monosulfonic acid was achieved exploring different synthetic approaches, along which the selection of the starting material resulted in a crucial point. Using PCB-153 (2,2'-4,4'-5,5'-hexachloro-1,1'-biphenyl) the synthesis afforded, as the major species, a side compound. On the contrary, the use of PCB-155 (2,2'-4,4'-6,6'-hexachloro-1,1'-biphenyl), a symmetric hexachlorobiphenyl derivative showing chlorine atoms at all the ortho positions, gave the target sulfonated-PCB compound. In this case, sulfonation was successfully carried out through a two-step procedure, involving chlorosulfonylation and the subsequent hydrolysis of the chlorosulfonyl intermediate.

Synthesis, Characterization and DNA-Binding Affinity of a New Zinc(II) Bis(5-methoxy-indol-3-yl)propane-1,3-dione Complex.

The novel zinc(II) µ-oxo-bridged-dimeric complex [Zn2(µ-O)2(BMIP)2] (BMIP = 1,3-bis(5-methoxy-1-methyl-1H-indol-3-yl)propane-1,3-dione), 1, was synthetized and fully characterized. The spectral data indicate a zincoxane molecular structure, with the BMIP ligand coordinating in its neutral form via its oxygen atoms. Structural changes in 1 in dimethylsulfoxide (DMSO) were evidenced by means of spectroscopic techniques including infrared absorption and nuclear magnetic resonance, showing DMSO entrance in the coordination sphere of the metal ion. The resulting complex [Zn2(µ-O)2(BMIP)2(DMSO)], 2, readily reacts in the presence of N-methyl-imidazole (NMI), a liquid-phase nucleoside mimic, to form [Zn2(µ-O)2(BMIP)2(NMI)], 3, through DMSO displacement. The three complexes show high thermal stability, demonstrating that 1 has high affinity for hard nucleophiles. Finally, with the aim of probing the suitability of this system as model scaffold for new potential anticancer metallodrugs, the interactions of 1 with calf thymus DNA were investigated in vitro in pseudo-physiological environment through UV-Vis absorption and fluorescence emission spectroscopy, as well as time-resolved fluorescence studies. The latter analyses revealed that [Zn2(µ-O)2(BMIP)2(DMSO)] binds to DNA with high affinity upon DMSO displacement, opening new perspectives for the development of optimized drug substances.