Synthesis, Spectroscopic Characterization and Photoactivity of Zr(IV) Phthalocyanines Functionalized with Aminobenzoic Acids and Their GO-Based Composites

Abstract

Two complexes of bis(aminobenzoato)zirconium(IV) phthalocyanine and their graphite oxide-based composites were synthesized and characterized in respect of their photochemical properties. Structures of phthalocyanines were confirmed by Mass and infrared spectroscopies. The absorption and photoluminescence spectra were investigated to show various behavior of the complexes in different media (dimethyl sulfoxide and saline). Optical technique (monitoring variation of absorption spectra of diphenylisobenzofuran used as an indicator) was used to prove the generation of reactive oxygen species (ROS) by under light irradiation in the range of the first biological window. The photoactivity of the materials was compared and discussed in terms of their potential ability to be used in biomedical applications, for example, as photosensitizers in photodynamic therapy.

Composites based on graphite oxide and zirconium phthalocyanines with aromatic amino acids as photoactive materials

“…S3 and S4 in Supplementary Information). Other identified signals are at m/z = 899.26 for PcZr(ASA) and m/z = 928.74 for PcZr(APhA)-their presence indicates that two solvent molecules (DMF) enter the coordinating sphere of zirconium, which confirms our earlier research on complexes of axially substituted zirconium phthalocyanines (Tahershamsi et al 2020;Tretyakova 2007). Fragmentation of the complex takes place in the following mode: in the first stage, the axial ligand is disconnected and a PcZrO 2 complex is formed with m/z = 637.78, followed by demetallation of the complex confirmed by the presence of the signal of free phthalocyanine at m/z = 515.82.…”

“…Admittedly, agglomeration is observed at quite high concentrations (above 10 -4 M), but it does occur. It is interesting that for PcZr(ASA), and for none of the previously studied complexes (Tahershamsi et al 2020;Gerasymchuk et al 2004;Tomachynski et al 2008;Tretyakova et al 2007), agglomeration in DMSO was not observed in a much wider range of concentrations. It is associated, in our opinion, with the nature of the axial ligand, which, in contrast to those previously studied, has more hydrophobic character.…”

“…(1) Graphite oxide-a nanosized carrier and catalyst of silver nanoparticles (Ag-NPs) formation, which shows antibacterial properties and enhances the antimicrobial activity of silver (Gerasymchuk et al 2017;Lukowiak et al 2019;Tahershamsi et al 2020;Kędziora et al 2013;Saladino et al 2020); (2) Ag-NPs-the antibacterial activity of silver is well known, but when the silver is in the form of nanoparticles, this action is more efficient due to an increased contact area further magnified by the GO presence (Kędziora et al 2013;Kędziora et al 2020); (3) Zirconium(IV) phthalocyanine complex (ZrPc) with axial ligands-macrocyclic water soluble metal complex (dye) which plays a role of a photosensitizer and generates singlet oxygen upon light irradiation (Tomachinski et al 2003;Tomachynski et al 2004;Gerasymchuk et al 2021).…”

“…In the previous studies, we have used bissubstituted (i.e. containing two axial ligands coordinated to the central metal atom of metal-phthalocyanine) zirconium phthalocyanine complexes, L 2 ZrPc, where L = L-lysine, L-arginine, 4-aminobutyric, 11-aminoundecanoic, 3-aminobenzoic, 2,5-diaminobenzoic, nicotinic and isonicotinic acids (Gerasymchuk et al 2017;Lukowiak et al 2019;Tahershamsi et al 2020;Kędziora et al 2013), which are representing different types of amino acids-aliphatic, aromatic, heterocyclic, and naturally occurring L-α-amino acids.…”

The Impact of Graphite Oxide Nanocomposites on the Antibacterial Activity of Serum

“…The following samples described in detail previously [ 9 , 29 , 44 , 45 ] were tested in this study: pure graphite oxide (GO), GO-PcZr(Lys) 2 -Ag (0.5 g/10 mL) (IV), GO-Ag (0.5 g/10 mL) (V), and GO-PcZr(Lys) 2 (VI). A brief scheme of composites preparation is shown in Figure 9 .…”