Superelectrophilic Activation of Phosphacoumarins towards Weak Nucleophiles via Brønsted Acid Assisted Brønsted Acid Catalysis.

The electrophilic activation of various substrates via double or even triple protonation in superacidic media enables reactions with extremely weak nucleophiles. Despite the significant progress in this area, the utility of organophosphorus compounds as superelectrophiles still remains limited. Additionally, the most common superacids require a special care due to their high toxicity, exceptional corrosiveness and moisture sensitivity. Herein, we report the first successful application of the "Brønsted acid assisted Brønsted acid" concept for the superelectrophilic activation of 2-hydroxybenzo[e][1,2]oxaphosphinine 2-oxides (phosphacoumarins). The pivotal role is attributed to the tendency of the phosphoryl moiety to form hydrogen-bonded complexes, which enables the formation of dicationic species and increases the electrophilicity of the phosphacoumarin. This unmasks the reactivity of phosphacoumarins towards non-activated aromatics, while requiring only relatively non-benign trifluoroacetic acid as the reaction medium.

Synthesis and Anticancer Evaluation of Novel 7-Aza-Coumarine-3-Carboxamides.

Herein, we report the design and synthesis of novel 7-aza-coumarine-3-carboxamides via scaffold-hopping strategy and evaluation of their in vitro anticancer activity. Additionally, the improved non-catalytic synthesis of 7-azacoumarin-3-carboxylic acid is reported, which features water as the reaction medium and provides a convenient alternative to the known methods. The anticancer activity of the most potent 7-aza-coumarine-3-carboxamides against the HuTu 80 cell line is equal to that of reference Doxorubicin, while the selectivity towards the normal cell line is 9-14 fold higher.

Diastereoselective Synthesis of Novel Spiro-Phosphacoumarins and Evaluation of Their Anti-Cancer Activity.

Herein we present the regio- and diastereoselective synthesis of novel pyrrolidine-fused spiro-dihydrophosphacoumarins via intermolecular [3 + 2] cycloaddition reaction. The presented approach is complementary to existing ones and provides an easy entry to the otherwise inaccessible derivatives. Additionally, the unprecedented pathway of the reaction of 4-hydroxycoumarin with azomethine ylides is described. The anti-cancer activity of the obtained compounds was tested in vitro, the most potent compound being 2.6-fold more active against the HuTu 80 cell line than the reference 5-fluorouracil, with a selectivity index > 32.

Electric Energy Storage Effect in Hydrated ZrO2-Nanostructured System.

The dimensional effect of electric charge storage with a density of up to 270 µF/g by the hydrated ZrO2-nanoparticles system was determined. It was found that the place of localization of different charge carriers is the generalized heterophase boundary-nanoparticles surface. The supposed mechanism of the effect was investigated using the theory of dispersed systems, the band theory, and the theory of contact phenomena in semiconductors, which consists of the formation of localized electronic states in the nanoparticle material due to donor-acceptor interaction with the adsorption ionic atmosphere. The effect is relevant for modern nanoelectronics, microsystem technology, and printed electronics because it allows overcoming the basic physical restrictions on the size, temperature, and operation frequency of the device, caused by leakage currents.

Growth characteristics of human bone marrow mesenchymal stromal cells at cultivation on synthetic polyelectrolyte nanofilms in vitro.

This study examines the adhesive properties and cytotoxicity of polyelectrolyte nanofilms from polyethyleneimine (PEI), polyallylamine hydrochloride (PAH) and sodium polystyrene sulfonate (PSS) on human bone marrow mesenchymal stromal cells (h-MSCs) and mouse adipose tissue (m-MSC) in vitro. Films are formed on 24- and 96-well culture plates in the combinations: PEI, PAH, PEI-PSS, PEI-PSS-PAH, PEI-PSS-PEI. An analysis of the culture results show that direct contact of h-MSCs with the PEI surface promotes adhesion (93-95% of adhesive cells versus 40% in the control). On the PEI surface, h-MSCs are evenly distributed, form colonies and 80% monolayer after 72 h of culture, as in the control on culture plastic. On nanofilms from PAH and PEI-PSS-PAH, cells grow in the form of rosette-like colonies with long and thin processes similar to neurites. The cytotoxic properties of PSS were revealed in direct contact with h-MSCs (more than 40% of nonviable cells with damaged plasma membranes). On the PSS surface, cells lost their adhesiveness. To culture and stably grow the cell mass of h-MSCs, it is better to use monolayer nanofilms made of highly adhesive and non-toxic PEI polyelectrolyte, which can bind the growth factors of blood serum and platelet lysate, ensuring the growth of h-MSCs under in vitro deprivation conditions.