Novel symmetrical and unsymmetrical fluorine-containing metallophthalocyanines: synthesis, characterization and investigation of their biological properties.

In this study, a new fluorinated phthalonitrile compound namely 5-bis[4-(trifluoromethoxy)-thiophenyl] phthalonitrile was synthesized. In addition, peripherally substituted symmetric metallated phthalocyanine derivatives [M = Co (2) and M = Zn (3)] and unsymmetrically substituted zinc phthalocyanine (ZnPc) complex (4) were synthesized by cyclotetramerization of this phthalonitrile compound. Characterization of all new compounds was carried out using FT-IR, NMR, UV-Vis, and mass spectroscopy. Additionally, antioxidant activity, DNA cleavage activity, antimicrobial activity, biofilm inhibition activity, and bacterial viability inhibition test of the compounds (1-4) were investigated. The antioxidant activities of the new phthalocyanine complexes were studied by performing two different methods. The results indicated that the highest DPPH (1,1-diphenyl-2-picrylhydrazyl) free radical scavenging activity was determined to be 67.85% for 2 and also 3 showed the highest activity with 31.65% for chelating activity at 200 mg L-1 concentration. Phthalocyanine compounds demonstrated effective DNA cleavage and antimicrobial activities. The highest percentage of cell vitality inhibition was found for compound 4, 56.92%. Also, test compounds exhibited good biofilm inhibition activity.

Investigation of the biological and photophysicochemical properties of new non-peripheral fluorinated phthalocyanines.

This study presents the synthesis of a series of new tetra-substituted phthalocyanines bearing 3,5-bis(trifluoromethyl)phenoxy groups at non-peripheral positions. The resulting macromolecules were characterized by performing different spectroscopic methods including 1H NMR, UV-Vis, FT-IR, and mass spectroscopy. In this study, the synergistic effect of phthalocyanines used as colorants in ink formulas with other chemicals available was probed for the first time. The synergistic effect of methyl laurate on the biological and antioxidant activities of the compounds (2-5) was investigated. Moreover, the therapeutic properties of the complexes (3, 6, and 7) were investigated using photochemical methods. Upon comparison, complex 7 (ΦΔ = 0.42) was found to be more effective than complex 6 (ΦΔ = 0.40) and complex 3 (ΦΔ = 0.27) in terms of producing singlet oxygen. The results confirmed that the heavy atom effect improves the therapeutic effects.

Effect of Position and Connected Atom on Photophysical and Photochemical Properties of Some Fluorinated Metallophthalocyanines.

This study presents the preparation of a new phthalonitrile derivative namely 3-(4-(trifluoromethoxy)thiophenoxy)phthalonitrile (1) and a series of its metallated phthalocyanines (M = Zn (II) (1a) and In(III) (1b)). In addition, the peripheral analog of the indium phthalocyanine chloride (2b) was newly synthesized. Characterization of the resulting compounds was carried out by utilizing various spectroscopic methods such as FT-IR, 1 H NMR and UV-Vis spectroscopy. The influence of concentration on aggregation properties of compound 1a was investigated at different concentrations of DMSO. The effect of solvent type on aggregation properties of compound 1a was studied, as well. According to the referred procedures, the macrocyclic molecules (2a, 3a-b and 4a-b) were prepared. The effect of some parameters including metal ion, the position of the substituent and the connected atom (oxo or thio) on photochemical and photophysical features of compounds (1a-b, 2a-b, 3a-b, and 4a-b) was studied for evaluation of their potential as a photosensitizer in PDT, comparatively. The highest singlet oxygen quantum yields (ΦΔ  = 0.71 for 1a and 0.80 for 2b) were obtained for complexes 1a and 1b in DMSO. The photophysical and photochemical features of the studied macromolecules are therefore suitable for photodynamic therapy applications.

Investigation of tyrosinase enzyme (from mushroom) inhibitory activities and antioxidant properties of new fluorine-containing phthalocyanines.

A series of new peripherally or nonperipherally substituted phthalocyanines bearing 4-(trifluoromethoxy)thiophenyl groups was synthesized. In addition, a new metal-free phthalocyanine bearing 4-(trifluoromethoxy)phenoxy on the nonperipheral position was prepared. The resulting phthalocyanines were characterized using some spectroscopic techniques such as 1 H nuclear magnetic resonance, Fourier-transform infrared spectroscopy, and UV-Vis spectroscopy, together with elemental analysis. When the tyrosinase enzyme inhibition activities of the synthesized phthalocyanines were examined, molecules 2b and 3b showed an inhibitory activity against the enzyme with IC50 values of 176.2 ± 0.65 and 284.4 ± 1.03, respectively. The inhibition types of the molecules and standard inhibitor kojic acid were found as competitive for 2b, mixed for 1b and kojic acid, and uncompetitive for 3b. Antioxidant activities were also assessed by using 1,1-diphenyl-2-picrylhydrazyl (DPPH) and reducing power assays, and the molecules showed moderate antioxidant activities.