The Synthesis, Characterization, Crystal Structure and Photophysical Properties of a New Meso-BODIPY Substituted Phthalonitrile.

A new highly fluorescent difluoroboradipyrromethene (BODIPY) dye (4) bearing an phthalonitrile group at meso-position of the chromophoric core has been synthesized starting from 4-(4-meso-dipyrromethene-phenoxy)phthalonitrile (3) which was prepared by the oxidation of 4-(2-meso-dipyrromethane-phenoxy)phthalonitrile (2). The structural, electronic and photophysical properties of the prepared dye molecule were investigated. The final product exhibit noticeable spectroscopic properties which were examined by its absorption and fluorescence spectra. The original compounds prepared in the reaction pathway were characterized by the combination of FT-IR, (1)H and (13)C NMR, UV-vis and MS spectral data. It has been calculated; molecular structure, vibrational frequencies, (1)H and (13)C NMR chemical shifts and HOMO and LUMO energies of the title compound by using B3LYP method with 6-311++G(dp) basis set, as well. The final product (4) was obtained as single crystal which crystallized in the triclinic space group P-1 with a = 9.0490 (8) Å, b = 10.5555 (9) Å, c = 11.7650 (9) Å, α = 77.024 (6)°, ß = 74.437 (6)°, γ = 65.211 (6)° and Z = 2. The crystal structure has intermolecular C-H···F weak hydrogen bonds. The singlet oxygen generation ability of the dye (4) was also investigated in different solvents to determine of using in photodynamic therapy (PDT).

Comparison of sonodynamic, photodynamic and sonophotodynamic therapy activity of fluorinated pyridine substituted silicon phthalocyanines on PC3 prostate cancer cell line.

BACKGROUND: Sonophotodynamic therapy (SPDT), a combination of photodynamic therapy (PDT) and sonodynamic therapy (SDT), may offer theraputic advantage. The therapeutic effects of sonodynamic, photodynamic, and sonophotodynamic of 5-(trifluoromethyl)-2-thiopyridine substituted silicon phthalocyanine (gy3) and its quaternized derivative (gy3q) were examined in vitro on prostate cancer using PC3 cells. METHODS: The SDT, PDT and SPDT efficiency was determined by using MTT test.Apoptosis mechanism was evaluated by HOPI staining. RESULTS AND DISCUSSIONS: According to MTT results, the phthalocyanines decreased cell viability when compared with a control group. Also, apoptosis measurement data represents that the phthalocyanines would produce much better therapeutic outcomes compare to PDT and SDT by utilizing SPDT. Further studies should be performed to understand the effectiveness of SPDT.

Synthesis of axially Schiff base new substituted silicon phthalocyanines and investigation of photochemical and sono-photochemical properties.

Sono-photodynamic therapy, which show a very high therapeutic effect compared to photodynamic therapy, is a newer method for anticancer treatments. However, unlike Photodynamic therapy (PDT), the number of studies measuring the efficiency of singlet oxygen for the Sono-photodynamic therapy (SPDT) method is quite insufficient in the literature. Therefore, this study aimed to synthesis novel axially substituted silicon (IV) phthalocyanines containing imine groups with improved photochemical properties and then reported the efficiency of singlet oxygen by both of photochemical and sono-photochemical studies. According to the results, the substituent group increased the singlet oxygen yield of silicon (IV) phthalocyanine dichloride and the sono-photochemical effect increased the singlet oxygen yields (ΦΔ=0.35 for 2a, 0.69 for 2b in photochemical study, 0.78 for 2a, 0.97 for 2b in sono-photochemical study).This article may pave the way to achieve high singlet oxygen efficiency.

Ultrasound versus Light: Exploring Photophysicochemical and Sonochemical Properties of Phthalocyanine-Based Therapeutics, Theoretical Study, and In Vitro Evaluations.

Photodynamic therapy (PDT) applications carried out with the assistance of ultrasound have attracted significant attention in recent years. The use of phthalocyanines, which are an important component as photosensitizers in PDT, is becoming more important day by day. In therapeutic applications, phthalocyanines can promote the production of reactive oxygen species. Motivated by this fact, the syntheses of metal-free (2), gallium (3), and indium (4) phthalocyanines have been achieved by substituting 4-(cinnamyloxy)phthalonitrile for the first time to evaluate their therapeutic applications. Additionally, photophysicochemical, sonophotochemical, and in vitro evaluations of phthalocyanines have been reported. To the best of our knowledge, this is the first study of the use of phthalocyanines with different metal ions as potential photosensitizers for sonophotodynamic therapy (SPDT) applications in gastric cancer cell lines. The results show that the quantum yield of the generation of singlet oxygen increased in sonophotochemical studies (ΦΔ = 0.55 (2), 0.85 (3), 0.96 (4)), compared to photochemical studies (ΦΔ = 0.22 (2), 0.61 (3), 0.78 (4)). The density functional theory (DFT) results are in good agreement with the experimental results and suggest increased reactivity of phthalocyanines 3 and 4 in various redox processes, thus implying their applicability and usefulness as potential therapeutic agents. These phthalocyanines are effective sensitizers for PDT, sonodynamic therapy (SDT), and SPDT against MKN-28 gastric cancer cell line in vitro. All three treatments decreased cell viability and induced apoptosis in the gastric cancer cell line. However, indium phthalocyanine (4)-mediated SPDT was a more effective treatment modality compared to indium phthalocyanine (4)-mediated PDT and SDT. Also, indium phthalocyanine (4) was found to be a more effective sensitizer to activate apoptosis compared to the other phthalocyanines. To sum up, phthalocyanine-mediated SPDT enhances the cytotoxic effect on gastric cancer cells more than the effect of SDT or PDT alone.

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.

Pegylated metal-free and zinc(II) phthalocyanines: synthesis, photophysicochemical properties and in vitro photodynamic activities against head, neck and colon cancer cell lines.

In this study, a series of peripherally and non-peripherally tetra-substituted metal-free and zinc(II) phthalocyanines were successfully prepared in good yields by cyclotetramerization of the phthalonitrile derivative bearing a tetraethylene glycol methyl ether group at 3- and 4- positions. All newly synthesized compounds were characterized using spectroscopic methods, such as FT-IR, NMR, mass and UV-Vis spectroscopy. To determine the therapeutic potential of the synthesized phthalocyanines, the effects of the substitution pattern (peripheral and non-peripheral) and central metal atom on the photophysicochemical properties were investigated. When comparing their singlet oxygen generation capabilities (ΦΔ), metallo-phthalocyanine derivatives with zinc (0.73 for 1b and 0.70 for 2b) showed higher singlet oxygen yield than metal-free derivatives (0.21 for 1a and 0.12 for 2a) in DMSO. The photodynamic therapy activities of the water-soluble phthalocyanines were tested via in vitro studies using the A253, FaDu (head and neck cancer cell lines), and HT29 (colon cancer) cell lines. The strongest photodynamic activity was found in 1b and 2b molecules with a metal core among the four molecules studied. The results suggested that the non-peripherally tetra-substituted 1b molecule was regarded as a suitable photodynamic therapy agent due to its light cytotoxicity and secondary impact induced by ROS production.

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).

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.

Novel axially carborane-cage substituted silicon phthalocyanine photosensitizer; synthesis, characterization and photophysicochemical properties.

The novel axially dicarborane substituted silicon (IV) (SiPc-DC) phthalocyanine was synthesized by treating silicon phthalocyanine dichloride SiPc(Cl)2 (SiPc) with o-Carborane monool. The compound was characterized by mass spectrometry, UV-Vis, FT-IR, (1)H and (11)B Nuclear Magnetic Resonance Spectroscopy (NMR). Spectral, photophysical (fluorescence quantum yield) and photochemical (singlet oxygen (ΦΔ) and photodegradation quantum yield (Φd)) properties of the complex were reported in different solutions (Dimethyl sulfoxide (DMSO), Dimethylformamide (DMF) and Toluene). The results of spectral measurements showed that both SiPc and carborane cage can have potential to be used as sensitizers in photodynamic therapy (PDT) and boron neutron capture therapy (BNCT) by their singlet oxygen efficiencies (ΦΔ=0.41, 0.39).