Cyano-Aryl Porphyrazine Pigments with Polycyclic Substituents as the Promising Agents for Photodynamic Therapy and Potential Sensors of Local Viscosity

Abstract

The unique cyanoporphyrazine pigment with four bulky phenanthrenyl peripheral substituents has been prepared. It demonstrates the noticeable shift of Q-band to longer wavelengths due to phenanthryl aromatic system extension. The compound showed very strong predominance of photoinduced cytotoxicity over cytotoxicity in the dark. The presented results indicate the enhancement of photodynamic properties of porphyrazine containing polycyclic aryl substituents in peripheral framing. It is confirmed that the chemical design of the peripheral aryl groups is an efficient toolkit for a fine tuning of photodynamic properties. Furthermore, we have shown that in spite of the presence of bulky substituents new cyano-aryl porphyrazine demonstrates the properties of fluorescent molecular rotors, i.e. the segmental intramolecular mobility in environment of low viscosity. Previously on the example of related cyano-aryl porphyrazines combining the properties of fluorescent molecular rotors and photosensitizers we have demonstrated high potential of these compounds as the sensors of local viscosity and rigidity of biological submicrometer environment within a living cell. So, in respect to PDT it can be a significant expansion of photosensitizer functionality as a potential agent of optical theranostics.

Cyanoarylporphyrazines with High Viscosity Sensitivity: A Step towards Dosimetry-Assisted Photodynamic Cancer Treatment

“…Two tetracyanotetra(aryl)porphyrazine dyes were tested with 4-biphenyl ( pz II ) and 4-diethylaminophenyl ( pz IV ) groups in the periphery of the porphyrazine macrocycle. For the synthesis of pz II and pz IV , we used a synthetic approach using a metal template assembly of the porphyrazine frameworks that we developed and described in detail previously [ 20 , 21 , 26 ]. The chemical structure of the dyes is shown in Figure 1 .…”

“…The fluorescence lifetime of pz II and pz IV in ethanol–glycerol solutions was measured according to the previously developed protocol described in [ 21 ]. Fluorescence was excited by a SC-450 laser picosecond pulsed source (Fianium Ltd., Southampton, UK) equipped with band-pass interference filters (ChromaTech., Michigan, USA) to select the wavelength range of 580–595 nm.…”

“…We recently reported the novel group of tetracyanotetra(aryl)porphyrazines (hereinafter, pz ) as prospective photosensitizers for PDT [ 20 , 21 , 22 , 23 , 24 ]. The structure of pz determines their unique photophysical properties; namely, an ability to induce the production of strongly cytotoxic singlet oxygen combined with high viscosity sensitivity of the fluorescence parameters [ 20 ].…”

“…In viscous media, the rotating is inhibited, resulting in a drastic increase in fluorescence intensity and fluorescence lifetime. We should underline that modification of the peripheral aryl groups coupled with a macrocycle core can significantly affect the photophysical and cytotoxic properties of pz , thus opening new prospects for fine-tuning of pz as an effective tool for PDT treatment [ 21 , 22 , 23 , 24 ].…”

Influence of physical properties of injectable drugs based on Florfenicol and on the adaptability of application in animal husbandry

“…The dynamic viscosity of the preparations (Pa•s) can be determined according to Stokes' law [9,10] according to the calculation scheme (Fig. 1).…”