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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. [ABSTRACT FROM AUTHOR]

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). [ABSTRACT FROM AUTHOR]

[Display omitted] • The synthesized phthalocyanines with cysteine-functionalized graphene quantum dots (cys-GQDs) for the first time. • Determination of photo-physicochemical properties of highly soluble zinc phthalocyanines. • Comparison of sonochemical, photochemical and sono-photochemical methods in singlet oxygen production. Current PDT agents often suffer from low singlet oxygen quantum yields, photobleaching, and poor biocompatibility. To address these issues, we propose novel PDT agents that combine the synthesized phthalocyanines with cysteine-functionalized graphene quantum dots (cys-GQDs) for the first time. This combination aims to enhance singlet oxygen production and improve solubility in biological media. In this way, new zinc phthalocyanines with halogen substituents were synthesized for potential use in photodynamic therapy (PDT). Specifically, 2-Bromo-4-methylphenol zinc (II) phthalocyanine (2a) and 2-chloro-4-methylphenol zinc(II) phthalocyanine (2b) and their graphene quantum dots derivatives were synthesized and characterized. The photochemical, sonochemical, and sono-photochemical properties of these compounds were analyzed, focusing on their efficiency in singlet oxygen production. Our studies of the 2a @cys-GQDs and 2b @cys-GQDs conjugates demonstrated higher singlet oxygen yields, suggesting their enhanced potential for clinical applications. [ABSTRACT FROM AUTHOR]

This work describes the synthesis, spectral and fluorescence properties of bis 4-(4-formyl-2,6-dimethoxyphenoxy) substituted zinc (ZnPc) and magnesium (MgPc) phthalocyanines. The new compounds have been characterized by elemental analysis, UV-Vis, FT-IR, 1H-NMR and mass spectra. Afterward, the effects of including metal ion on the photophysicochemical properties of the complexes were studied in biocompatible solvent DMSO to analyze their potential to use as a photosensitizer in photodynamic therapy (PDT). The fluorescence and singlet oxygen quantum yields were calculated as 0.04–0.15 and 0.70–0.52 for ZnPc and MgPc, respectively. According to the results, MgPc has higher fluorescence quantum yield than ZnPc, while ZnPc has higher singlet oxygen quantum yield than MgPc. The results show that the synthesized complexes can have therapeutic outcomes for cancer treatment. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

This study reports synthesis of three new metallophthalocyanines namely 1(4),8(11),15(18),22(25)‐tetrakis‐(4‐(trifluoromethoxy)phenoxy) phthalocyaninato} Gallium chloride (1‐Ga), {2(3),9(10),16(17),23(24)‐tetrakis‐(4‐(trifluoromethoxy)phenoxy)phthalocyaninato} Gallium chloride (2‐Ga), and {2,3,9,10,17,18,23,24‐octakis‐(4‐(trifluoromethoxy)phenoxy)phthalocyaninato} Gallium chloride (3‐Ga). The newly synthesized macromolecules were characterized using different spectroscopic approaches, such as Fourier‐transform infrared (FT‐IR), ultraviolet–visible (UV–vis), and mass (MS) spectroscopy. Aggregation properties of the resulting compounds were studied at different concentrations ranging from 4 × 10−6 to 14 × 10−6 M. Density functional theory level computations were conducted to shed light on their electronic properties. The effect of the number and position of the substituent on photophysicochemical properties of the gallium chloride complexes (1‐Ga, 2‐Ga, and 3‐Ga) was studied for the examination of their performance as photosensitizer candidates in photodynamic therapy (PDT), comparatively. The complex 3‐Ga shows up the highest singlet oxygen quantum yield (ΦΔ = 0.87). The photophysical and photochemical features of the stated compounds are useful for PDT applications. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

• Synthesis and characterization of new substituted silicon phthalocyanine. • Comparison of singlet oxygen efficiency obtained by different methods. • Determination of photophysico-chemical properties of silicon phthalocyanines. Nowadays, non-invasive and nontoxic therapy methods are preferred to treat diverse types of cancer. Sono-photodynamic therapy (SPDT) is one of these alternative methods, combining the properties of PDT (photodynamic therapy) and SDT (sonodynamic therapy) and resulting in a higher singlet oxygen generation. The efficiency of this method is increased by synthesizing a complex with enhanced photochemical properties to use as a sensitizer. Phthalocyanines, especially with added derivatives holding diamagnetic metals such as Si4+, are often compounds used in PDT studies owing to their efficient yields of singlet oxygen formation. In this study, 4‑hydroxy-7-methoxyquinoline silicon phthalocyanine was synthesized and its anti-cancer therapy effect rates were calculated and compared by photochemical and sono-photochemical methods in DMSO. This research will help the studies that aim to obtain high singlet oxygen efficiency in therapeutic methods. [Display omitted] [ABSTRACT FROM AUTHOR]

Singlet oxygen quantum yield is known as a suitable measure to study the oxygen-producing capacity of a sono/photosensitizing molecule. Its value significantly depends on the applied therapeutic method and the photophysicochemical properties of the molecule. To obtain a good sensitizer, this paper aims to synthesize highly soluble 3-[4-(4-fluoro-, chloro-, and bromo-phenoxy)phenoxy] substituted new indium phthlocyanines and then calculates the singlet oxygen generations by performing both photochemical and sono-photochemical methods in DMSO as a biocompatible solvent. The complexes showed higher singlet oxygen quantum yields (0.84 for InPc1 , 0.89 for InPc2 , and 0.94 for InPc3) by applying sono-photochemical methods compared to those (0.63 for InPc1 , 0.67 for InPc2 , and 0.80 for InPc3) were obtained by applying photochemical methods. These results show that the sono-photochemical methods improve the therapeutic activity in comparison to photochemical ones. • New three non-peripherally tetra-substituted chloroindium phthalocyanines bearing 3-[4-(4-fluoro-, chloro-, and bromo-phenoxy)phenoxy were synthesized and characterized. • For the first time photochemical and sono-photochemical properties of the complexes were investigated to determine the efficiencies of singlet oxygen. • Comparison of singlet oxygen efficiency obtained by sono-photochemical and photochemical methods. • The halogen atom effects were also investigated. [ABSTRACT FROM AUTHOR]

• Synthesis and characterization of di-axially 9(Hydroxymethyl)anthracene substituted silicon phthalocyanine. • Comparison of singlet oxygen efficiency obtained by sono-photochemical and photochemical methods. • Determination of aggregation and photophysico-chemical properties of highly soluble silicon phthalocyanine. Sono-photochemical study which combines photochemical and sonochemical studies is a favorable alternative modality to produce high singlet oxygen. However, though there are many articles about the calculation of singlet oxygen quantum yield for Photodynamic therapy (PDT) studies in the literature, there is no study to measure the efficiency of singlet oxygen for Sono-photodynamic therapy (SPDT) method. Therefore, this study aimed to synthesis a complex with improved photochemical properties and then calculates the efficiency of singlet oxygen by both of photochemical and sono-photochemical studies in DMSO and DMF. The designed complex showed remarkably high singlet oxygen quantum yields. The Φ Δ values (0.74 in DMSO, 0.72 in DMF for photochemical study) reached to 0.96 in DMSO, 0.88 in DMF for sono-photochemical study and these results prove that SPDT improves the therapeutic activity due to the sono-photochemical effect. This article will lead to the studies that seek to obtain highly efficient singlet oxygen. Image, graphical abstract [ABSTRACT FROM AUTHOR]

• Synthesis of water-soluble tetra-substituted phthalocyanines containing sodium 2-mercaptoethanesulfonate substituents. • Photo-physicochemical and biological properties. • The effective inhibitor for the α-glycosidase, human carbonic anhydrase I and II isoforms, and cholinesterase enzymes. • Antidiabetic, anticancer and anticholinergic potentials. In this study, we have reported on the synthesis and characterization of water-soluble phthalocyanines [M=2H (2) , Zn(II) (3) , Ga(III)Cl (4) , containing sodium 2-mercaptoethanesulfonate substituents at the non-peripheral positions. All compounds were characterized by UV–vis, FT-IR and NMR spectroscopies, and MALDI-TOF mass spectra. Besides, spectral, photophysical (fluorescence quantum yields) and photochemical (singlet oxygen generation and photodegradation under light irradiation) properties of newly synthesized phthalocyanines were investigated in DMSO. These synthesized phthalocyanines [M=2H (2) , Zn(II) (3) , Ga(III)Cl (4) were found to be effective inhibitor compounds for the α-glycosidase, human carbonic anhydrase I and II (cytosolic, ubiquitous isozymes), hCA IX (transmembrane, cancerassociated isozyme), and cholinesterase enzymes with Ki values in the range of 0.66±0.08–2.31±0.24 μM for α-glycosidase, 8.54±1.63−14.93±2.05 μM for hCA I, 10.77±1.55−13.74±0.97 μM for hCA II, 10.55±0.98−15.96±1.54 μM for hCA IX, 102.77±16.04–158.43±26.95 μM for BChE, and 114.75±15.05–174.31±35.43 μM for AChE, respectively. Additionally, this work is also the first example of cancer-associated isozyme hCA IX inhibition by these novel phthalocyanines. [ABSTRACT FROM AUTHOR]

Phenanthroline substituted five-nuclear phthalocyanine zinc complex was synthesized and characterized. Photophysical, photochemical and sono-photochemical properties of symmetrical zinc phthalocyanine were investigated. Singlet oxygen efficiency was calculated by both photochemical and sono-photochemical methods. The Φ Δ value was calculated as 0.72 for photochemical method, the Φ Δ value reached to 0.98 for sono-photochemical method. [Display omitted] Sono-photodynamic therapy (SPDT) which is the combination of photodynamic therapy (PDT) and sonodynamic therapy (SDT) is an alternative and efficient method among cancer treatments achieving high singlet oxygen quantum yield. This study aimed to synthesize Schiff base substituted Zn phthalocyanine containing phenanthroline group to obtain suitable sono-photosensitizer. The target phthalocyanine (4) was obtained by cyclotetramerization reaction of phenanthroline-Zn(II) complex substituted phthalonitrile (3) with zinc acetate. The synthesized compounds were characterized by various spectroscopic techniques including FT-IR, Mass, UV–Vis, and 1H NMR spectroscopy. The singlet oxygen quantum yield was calculated in both photochemical and sono-photochemical method for compound 4. While the Φ Δ value was calculated as 0.72 for photochemical method, the Φ Δ value reached to 0.98 for sono-photochemical method. [ABSTRACT FROM AUTHOR]

• Single crystal x-ray diffraction measurements of 4-(1-methyl-1H-imidazole-2-thiol) phthalonitrile. • Synthesis of novel water-soluble phthalocyanine hydrochloride bearing imidazole derivative. • Investigation of photo-physicochemical, anti-α-glygosidase, anti-cholinesterases properties. • Antibacterial properties: gram-negative and gram-positive bacteria. In this work, we have reported on the synthesis and characterization of water-soluble hydrochloride forms (2a-4a) based on novel peripherally [ M = metal-free (2) , zinc (II) (3) , gallium (III) chloride (4) ] phthalocyanines bearing 1-methyl-1H-imidazole-2-thiol substituents. Characterization of all compounds used was supported by a series of spectroscopic techniques such as UV–Vis, FT-IR 1H NMR, 13C NMR and MALDI-MS, etc. The confirmation of the molecular structure of 4-(1-methyl-1H-imidazole-2-thiol) phthalonitrile (1) by single crystal x-ray diffraction experiment was performed for the first time in this work. Besides, the intra/inter-molecular interactions inside the obtained crystal structure have been investigated. Afterward, the effects of the central metal atoms and solvents on the photophysicochemical properties of the phthalocyanines were analyzed to investigate their potential to use as a photosensitizer in photodynamic theraphy (PDT). The obtained results show that the phthalocyanines have therapeutic outcomes for cancer treatment. It has been seen that all compounds have a better ability to inhibit compared to existing tried inhibitors. Among these, the best inhibitors against acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) enzymes are (4) (Ki 47.71±9.14 µM and IC 50 68.22) and (3a) (Ki 20.12±3.75 µM and IC 50 19.24), respectively. Also, against α-Glycosidase, (4) showed the highest effect (Ki 9.13±1.05 µM and IC 50 11.22). Phthalocyanines were performed to gram-negative and gram-positive bacteria using minimum inhibition concentration (MIC) assay and indicated an antibacterial effect. [Display omitted] [ABSTRACT FROM AUTHOR]

Graphical abstract This work presents the synthesis of peripherally and non-peripherally tetra-substituted metallophthalocyanines. The quantum chemical parameters of the ligands, such as the HOMO, LUMO and chemical hardness were calculated by the B3lyp, HF and M062x methods. The Δ G value of the phthalocyanine compunds were calculated with the obtained results. In addition, the photophysical and photochemical properties of the newly synthesized phthalocyanines were investigated in DMSO solutions, comparatively. Abstract This work presents the synthesis of peripherally and non-peripherally tetra-substituted metallophthalocyanines (6 – 14) containing the 2-(3,4-dimethoxyphenyl)ethanol group. The synthesized compounds were characterized by standard spectroscopy methods. The ligands of the metallophthalocyanines were investigated by quantum chemical calculations. The quantum chemical parameters of these ligands (1 and 2) such as the HOMO, LUMO and chemical hardness were calculated by the B3lyp, HF and M062x methods. The Δ G value of the metal complexes of the ligands were calculated with the obtained results. In addition, photophysical (fluorescence quantum yields) and photochemical (singlet oxygen generation and photodegradation under light irradiation) properties of newly synthesized phthalocyanines were investigated in DMSO solutions, comparatively. [ABSTRACT FROM AUTHOR]