Biological Performance of Hexadeca-Substituted Metal Phthalocyanine/Reduced Graphene Oxide Nanobioagents.

This study presents a tetra-substituted phthalonitrile derivative, namely, diethyl 2-(3,4-dicyano-2,5-bis(hexyloxy)-6-(4-(trifluoromethoxy)phenoxy)phenyl)malonate (a), cyclotetramerizing in the presence of some metal salts. The resultant hexadeca-substituted metal phthalocyanines [M= Co, Zn, InCl)] (b-d) were used for the modification of reduced graphene oxide for the first time. The effect of the phthalonitrile/metal phthalocyanines on biological features of reduced graphene oxide (rGO) was extensively examined by the investigation of antioxidant, antimicrobial, DNA cleavage, cell viability, and antibiofilm activities of nanobioagents (1-4). The results were compared with those of unmodified rGO (nanobioagent 5), as well. Modification of reduced graphene oxide with the synthesized compounds improved its antioxidant activity. The antioxidant activities of all the tested nanobioagents also enhanced as the concentration increased. The antibacterial activities of all the nanobioagents improved by applying the photodynamic therapeutic (PDT) method. All the phthalonitrile/phthalocyanine-based nanobioagents (especially phthalocyanine-based nanocomposites) exhibited DNA cleavage activities, and complete DNA fragmentation was observed for nanobioagents (1-4) at 200 mg/L. They can be used as potent antimicrobial and antimicrobial photodynamic therapy agents as well as Escherichia coli microbial cell inhibitors. As a result, the prepared nanocomposites can be considered promising candidates for biomedicine.

Photophysicochemical and Biological Properties of New Phthalocyanines Bearing 4-(trifluoromethoxy)phenoxy and 2-(4-methylthiazol-5-yl)ethoxy Groups on Peripheral Positions.

As thiazoles and fluorinated groups are well known as active species of hybrid pharmaceutical agents, this study aimed to evaluate the synergic effect of these groups on the biological features of phthalocyanines for the first time in the hope of discovering efficient pharmaceutical agents. Therefore, a new phthalonitrile derivative namely 4-(2-(4-methylthiazol-5-yl)ethoxy)-5-(4-(trifluoromethoxy)phenoxy)phthalonitrile (1) and its metal-free (2)/metal phthalocyanines (3-5) were prepared and characterized using various spectroscopic techniques. Solubility of new phthalocyanines (2-5) was examined in a series of polar and nonpolar solvents. Additionally, sono/photochemical methods were applied to examine the photophysical and sono/photochemical properties of new zinc phthalocyanine to measure its potential as a probable material for sono/photodynamic therapies. The antioxidant activities of compounds (1-5) were evaluated using the DPPH scavenging activity method and the highest radical scavenging activity was obtained 92.13% (200 mg L-1 ) for manganese phthalocyanine. All the phthalocyanines demonstrated high DNA nuclease activity, as well. The antimicrobial activities of compounds (1-5) were investigated using disk diffusion and microdilution methods. The phthalocyanines exhibited effective microbial cell inhibition activity against Escherichia coli (E. coli). Antimicrobial photodynamic therapy activity was investigated against E. coli by LED irradiation. Compounds (2-5) acted as photosynthesizers. Also, they displayed significant biofilm inhibition activity against Staphylococcus aureus (S. aureus) and Pseudomonas aeruginosa (P. aeruginosa).

Photophysicochemical, sonochemical, and biological properties of novel hexadeca-substituted phthalocyanines bearing fluorinated groups.

This study presents the preparation of a novel tetra-substituted phthalonitrile (1), namely, 3,6-bis(hexyloxy)-4,5-bis(4-(trifluoromethoxy)phenoxy)phthalonitrile (1) and its metal-free (2)/metal {M = Zn (3), Cu (4), Co (5), Lu(CH3COO) (6), Lu (7)} phthalocyanines. A series of various spectroscopic methods (UV-vis, FT-IR, mass, and 1H NMR spectroscopy) were performed for the characterization of the newly synthesized compounds. The potential of compounds 2, 3, and 6 as photosensitizing materials for photodynamic and sonophotodynamic therapies was evaluated by photophysical, photochemical, and sonochemical methods. The highest singlet quantum yields were obtained for the zinc phthalocyanine derivative 3 by performing photochemical and sonochemical methods. In addition, several biological activities of the new compounds 1-7 were investigated. The newly synthesized phthalocyanines exhibited excellent DPPH scavenging activity and also DNA nuclease activity. The antimicrobial activity of the new compounds was evaluated by the disc diffusion assay. Effective microbial cell viability inhibition was observed with phthalocyanine macromolecules. The photodynamic antimicrobial therapy of the phthalocyanines showed 100% bacterial inhibition when compared to the control. They also exhibited significant biofilm inhibition activity against S. aureus and P. aeruginosa. These results indicate that new phthalocyanines are promising photodynamic antimicrobial therapies for the treatment of infectious diseases.

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.