Chiral plasmonic response of 2D Ti3C2Tx flakes: realization and applications

The circularly polarized light sensitive materials response can be reached at plasmon wavelengths through the coupling of intrinsically non-chiral plasmonic nanostructure with chiral organic molecules. As a plasmonic background, the different types of metal nanoparticles of various shapes and sizes are successfully tested and an apparent circular dichroism (CD) signal is measured in both, nanoparticles suspensions and after nanoparticle immobilization in substrate. In this work, the creation of plasmon-active 2D flakes of MXenes (Ti3C2Tx) is proposed, with the apparent CD response at plasmon wavelength, through the coupling of intrinsically non-chiral flakes with helically shaped helicene enantiomers. This work provides the first demonstration of chiral and plasmon-active 2D material, which shows the absorption sensitive to light intrinsic circular polarization even in plasmon wavelengths range. The appearance of the induced CD signal is additionally confirmed by several theoretical calculations. After the experimental and theoretical confirmation of the optical chirality at plasmon wavelengths, the flakes are utilized for the polarization sensitive conversion of light to heat, as well as for polarization dependent triggering of plasmon-assisted chemical transformation

Oxidative Photocyclization of Aromatic Schiff Bases in Synthesis of Phenanthridines and Other Aza-PAHs

The oxidative photocyclization of aromatic Schiff bases was investigated as a potential method for synthesis of phenanthridine derivatives, biologically active compounds with medical applications. Although it is possible to prepare the desired phenanthridines using such an approach, the reaction has to be performed in the presence of acid and TEMPO to increase reaction rate and yield. The reaction kinetics was studied on a series of substituted imines covering the range from electron-withdrawing to electron-donating substituents. It was found that imines with electron-withdrawing substituents react one order of magnitude faster than imines bearing electron-donating groups. The 1H NMR monitoring of the reaction course showed that a significant part of the Z isomer in the reaction is transformed into E isomer which is more prone to photocyclization. The portion of the Z isomer transformed showed a linear correlation to the Hammett substituent constants. The reaction scope was expanded towards synthesis of larger aromatic systems, namely to the synthesis of strained aromatic systems, e.g., helicenes. In this respect, it was found that the scope of oxidative photocyclization of aromatic imines is limited to the formation of no more than five ortho-fused aromatic rings

Effect of fluorination on the pharmacological profile of 11β isomers of fulvestrant in breast carcinoma cells

We describe the synthesis of an 11beta isomer 3 of the steroidal antiestrogen fulvestrant 2. Partial fluorination of the 11beta side chain in 3 leads to 4, which still shows strong antiproliferative activity on MCF-7 cells. However, unlike 2 and 3, compound 4 fails to down-regulate estrogen receptor alpha (ERalpha). This result suggests that ERalpha down-regulation is not a sine qua non condition for the antitumor activity of steroidal antiestrogens.SCOPUS: ar.jinfo:eu-repo/semantics/publishe

Optimisation of the Photonic Efficiency of TiO2 Decorated on MWCNTs for Methylene Blue Photodegradation

MWCNTs/TiO2 nanocomposite was prepared by oxidising MWCNT in H2SO4/HNO3 then decorating it with TiO2-p25 nanopowder. The composites were characterised using XRD, TEM, FT-IR PL and UV-vis spectroscopy. The TEM images have shown TiO2 nanoparticles immobilised onto the sidewalls of the MWCNTs. The UV-vis spectrum confirms that the nanocomposites can significantly absorb more light in the visible regions compared with the commercial TiO2 (P25). The catalytic activity of these nanocomposites was determined by photooxidation of MB aqueous solution in the presence of visible light. The MWCNTs/TiO2 (1:3) mass ratio showed maximum degradation efficiency. However, its activity was more favourable in alkaline and a neutral pH than an acidic medium