Peripheral (E)-2-[(4-hydroxybenzylidene)-3,4-dihydronaphthalen-1(2H)-one)]-coordinated phthalocyanines with improved enzyme inhibition properties and photophysicochemical behaviors.

In this study, (E)-4-{4-[(1-oxo-3,4-dihydronaphthalen-2(1H)-ylidene)methyl]phenoxy}phthalonitrile (4) and its phthalocyanine derivatives (5-8) were synthesized for the first time. Aggregation behaviors of the novel soluble phthalocyanines in organic solvents were investigated. In addition, the efficiency of 1O2 production of (5) and ZnPc (6) was investigated. The singlet oxygen quantum yields (ΦΔ) for 2HPc (5) and ZnPc (6) were found to be 0.58 and 0.83, respectively. Additionally, novel phthalocyanines (5-8) were investigated for their ability to inhibit enzymes. They exhibited a highly potent inhibition effect on human carbonic anhydrase I and II (hCA I and II) and α-glycosidase (α-Gly) enzymes. Ki values are in the range of 2.60 ± 9.87 to 11.53 ± 6.92 µM, 3.35 ± 0.53 to 15.47 ± 1.20 µM, and 28.60 ± 4.82 to 40.58 ± 7.37 nM, respectively. The calculations of the studied molecule at the B3LYP, HF, and M062X levels in the 6-31G basis sets were made using the Gaussian package program. Afterward, the interactions occurring in the docking calculation against a protein that is the crystal structure of hCA I (PDB ID: 2CAB), the crystal structure of hCA II (PDB ID: 5AML), and the crystal structure of α-Gly (PDB ID: 1R47), were examined. Following that, Protein-Ligand Interaction Profiler (PLIP) analysis was used to look at the interactions that occurred during the docking calculation in further detail.

Correction: Evaluation of the effects of newly synthesized metallophthalocyanines on breast cancer cell lines with photodynamic therapy.

Correction for 'Evaluation of the effects of newly synthesized metallophthalocyanines on breast cancer cell lines with photodynamic therapy' by Hayrani Eren Bostanci et al., Dalton Trans., 2022, 51, 15996-16008, https://doi.org/10.1039/d2dt01912d.

Novel tetrakis-phthalocyanines bearing pyrimidine derivative: crystal XRD analysis, enzyme inhibition, molecular docking, and anticancer effects.

In this study, the novel 4-(4-Aminopyrimidin-2-ylthio) phthalonitrile (1) as starting material was synthesized and its 3D structure was verified by the single crystal X-ray diffraction experiment. Then, its peripherally tetra-substituted phthalocyanines (2,3) and the methylated derivatives (2a,3a) containing pyrimidine derivative were synthesized. All these newly synthesized compounds were characterized with various spectroscopic methods such as UV-Vis, FT-IR, 1H-NMR, 13C-NMR and MALDI-TOF MS by obtaining satisfactory results. In addition, these novel phthalocyanines effectively inhibited acetylcholinesterase enzyme, with Ki values in the range of 10.43 ± 2.38 to 41.70 ± 9.32 µM. For the related enzyme, the IC50 values were obtained in the range of 11.68 to 44.28 µM. For α-glycosidase enzyme the most effective Ki values of (3a) and (2) were with Ki values of 92.87 ± 10.70 and 95.18 ± 17.83 µM, respectively. Indeed, the most potent phthalocyanines against both enzymes were recorded for the purpose of investigating interaction modes of these complexes in the active site of the target enzyme. The cytotoxicity potential of these phthalocyanines against human breast, colon, and prostate cancers demonstrated that these compounds had normal cytotoxic effects.Communicated by Ramaswamy H. Sarma.

Evaluation of the effects of newly synthesized metallophthalocyanines on breast cancer cell lines with photodynamic therapy.

In this study, the new phthalonitrile derivative 3-(4-(3-oxobutyl)phenoxy)phthalonitrile (1) and its non-peripheral metallophthalocyanine derivatives [zinc (2), copper (3), cobalt (4), manganese (5), gallium (6), and indium (7)] were synthesized. The newly synthesized phthalocyanines were characterized by standard spectroscopic methods, such as FT-IR, 1H NMR, UV-Vis, fluorescence spectroscopies, and MALDI-TOF spectrometry. Aggregation behaviors of the novel phthalocyanines were investigated by UV-Vis spectroscopy. The effect of pH change on the electronic and emission spectra of the newly synthesized phthalocyanine derivatives was studied in THF media. The electronic spectra of the new zinc (2), copper (3), and cobalt (4) phthalocyanines exhibited bathochromic shifts in acidic pH values due to the presence of monoprotonated forms. Surprisingly, the same effect was not observed for manganese (5) and indium (7) phthalocyanines. On the other hand, gallium (6) showed a slight red-shifted band with the addition of HCl to the medium. Also, it was determined that the synthesized zinc (2) and gallium (6) phthalocyanines had a selective phototoxic effect on the MCF-7 breast cancer cell line compared to the MCF-10A healthy breast cell line. The IC50 values of zinc (2) and gallium (6) phthalocyanines were determined for MCF-7 and MCF-10A cell lines. The IC50 values of MCF-7 for compounds 2 and 6 were found to be 1.721 ± 0.4 µg mL-1 and 7.406 ± 0.32 µg mL-1, respectively. The IC50 values of MCF-10A for phthalocyanines 2 and 6 were found to be 48.90 ± 0.69 µg mL-1 and 14.77 ± 1.09 µg mL-1, respectively. In the LDH (lactate dehydrogenase)-ELISA study, the LDH levels that formed on a cellular basis after the application were measured, and it was observed that the cells were directed towards apoptosis. In addition, it was observed that cancer cells underwent more apoptosis than healthy cells as a result of this application with cell-cycle and dead cell kits performed by flow cytometry. This research shows that non-peripheral substituted gallium and zinc phthalocyanine derivatives (2 and 6) can be suitable photosensitizers for the photodynamic treatment of breast cancers.

Algaecidal and oxidative effects of metal-free phthalocyanine beta tetra-substituted with sodium 2-mercaptoethanesulfonate.

In this study, a water-soluble metal-free phthalocyanine (SPC) containing sodium 2-mercaptoethanesulfonate substituents at the peripheral positions was used to investigate the algaecidal properties and oxidative effects on the growth of two microalgal species, Arthrospira platensis and Chlorella vulgaris. Although OD at 560 nm and chlorophyll-a content were decreased in Arthrospira platensis during 7 days depending on dose and time, increases in both OD at 750 and chlorophyll-a content at 8 ppb (parts per billion) concentration on the 7th day were observed in Chlorella vulgaris. However, total SOD (superoxide dismutase) and GR (glutathione reductase) enzyme activity of A. platensis cultures did not display any alteration in all concentrations, SOD activity displayed an increase significantly at 2 ppb concentration, and GR activity showed increases at 1, 2, and 4 ppb concentrations in C. vulgaris application. In A. platensis application, APX (ascorbate peroxidase) activity decreased at 0.50 ppb, 1 ppb, and 1.5 ppb concentrations. In addition, C. vulgaris application showed decreases at all concentrations. When MDA content increased at all concentrations, the H2O2 content increased only at significatly 0.125 ppb concentration in A. platensis cultures. Both MDA (malondialdehyde) and H2O2 (hydrogen peroxide) content of C. vulgaris cultures showed a statistically significant decrease at all concentrations compared to control. Free proline decreased at 0.25 ppb, 0.50 ppb, 1 ppb, and 1.5 ppb concentrations in A. platensis application, and it decreased at all the concentrations of C. vulgaris application. It concluded that this compound has inhibition effects on A. platensis, but it supports growth in C. vulgaris. Therefore, this synthesized phthalocyanine compound (SPC) should be consumed carefully, and the contamination to aquatic ecosystems should be prevented.

Tetra-substituted phthalocyanines bearing thiazolidine derivatives: synthesis, anticancer activity on different cancer cell lines, and molecular docking studies.

In the first step, (4R)-2-(2-hydroxyphenyl)thiazolidine-4-carboxylic acid (c) and 2-(2-(3,4-dicyanophenoxy)phenyl)thiazolidine-4-carboxylic acid (1) were prepared. Then, the peripherally tetra-substituted metallophthalocyanines [ZnPc (2), CuPc (3), and CoPc (4)] were synthesized by using 1. The structures of the obtained compounds were characterized by common spectroscopic methods. Aggregation behaviors of the tetra-substituted metallophthalocyanines (2-4) were investigated by UV-Vis and fluorescence spectroscopy in the presence/absence of soft metal ions. The electronic spectra of the newly synthesized metallophthalocyanines [ZnPc (2), CuPc (3), and CoPc (4)] were analyzed by the Bayliss method. The fluorescence quantum yield of diamagnetic ZnPc (2) was obtained in DMSO at room temperature. Also, the anticancer activity of the newly synthesized metallophthalocyanine derivatives was studied on C6, DU-145, and WI-38 cell lines and investigated using six concentrations (3.125; 6.25; 12.5; 50; 75; 100 µg L-1). The cell cycle and apoptosis analyses of CuPc (3) were performed. In addition, the chemical and biological activities of 2-(2-(3,4-dicyanophenoxy)phenyl)thiazolidine-4-carboxylic acid (1) and its novel type metallophthalocyanines [ZnPc (2), CuPc (3), and CoPc (4)] were compared with many parameters obtained from the Gaussian software and molecular docking methods.

Synthesis, characterization and investigation of algal oxidative effects of water-soluble copper phthalocyanine containing sulfonate groups.

In this study, the chemical and algicidal properties of the newly synthesized compound (2) were evaluated and its algal oxidative effects were determined in Arthrospira platensis and Chlorella vulgaris. First, we have reported on the synthesis and characterization of highly water-soluble copper (II) phthalocyanine (2), containing sodium 2-mercaptoethanesulfonate (2) substituents at the peripheral positions. Some spectroscopic techniques were used to characterize the new synthesized compound (2). In terms of biological properties, C. vulgaris were more tolerance to compound (2) than A. platensis depending to growth parameters. When SOD (Superoxide dismutase) activity significantly increased at 0.25 ppb and 1.5 ppb concentrations in A. platensis cultures, it increased at 6 ppb concentration in C. vulgaris cultures. GR (Glutathione reductase) activity decreased at 1 ppb and 1.5 ppb concentrations while APX (Ascorbate peroxidase) activity did not show a significant change at any concentrations in A. platensis cultures. GR activity showed a significant increase at 6 ppb concentration, while APX activity increased at all concentrations compared to control in C. vulgaris cultures. MDA (malondialdehyde) and H2O2 content decreased at 1 and 1.5 ppb concentrations but there were significant increases in the proline content at all concentrations compared to the control in A. platensis. MDA, H2O2 and free proline contents showed a significant increase at 0.5 ppb concentration in C. vulgaris. In conclusion, compound (2) have algicidal effects, and also it causes to oxidative stress in these organisms.

α-Substituted phthalocyanines based on metal-induced H- or J-type aggregation for silver and palladium ions: synthesis, fluorescence, and antimicrobial and antioxidant properties.

In this study, firstly, 3-(2,3-bis(hexadecylthio)propoxy)phthalonitrile (2) as a new phthalonitrile derivative was prepared. Then, new types of non-peripheral phthalocyanine derivatives [CuPc (3), ZnPc (4), and CoPc (5)] were synthesized by using this ligand. The synthesized new compounds were characterized by common spectroscopic methods such as FTIR, 1H-NMR, 13C-NMR, MALDI-TOF, UV-Vis and fluorescence spectroscopy. The H- or J-type aggregation behaviors of novel type metallophthalocyanines in the presence of valuable metal ions such as Ag(i) and Pd(ii) were investigated by UV-Vis and fluorescence spectroscopy. The quenching efficiency of the Ag(i) and Pd(ii) ions for ZnPc (4) was obtained using the Stern-Volmer equation and the quenching constant of ZnPc (4) towards Ag(i) and Pd(ii) ions was found to be 2.9 × 105 mol L-1 and 1.2 × 105 mol L-1, respectively. The binding constant (Ka) and binding stoichiometry (n) of Ag(i) and Pd(ii) ions for ZnPc (5) were calculated using a modified Benesi-Hildebrand equation, and were found to be 1.4 × 108 M-1 and 3.4 × 107 M-1, respectively. The binding ratio and free energy change of Ag(i) and Pd(ii) ions for ZnPc (4) were found to be 1.86, 1.54, -46.49 kJ mol-1 and -42.9 kJ mol-1, respectively. Also, the antioxidant properties of the synthesized novel type metallophthalocyanines and their Ag(i) and Pd(ii) ion doped aggregates were determined using three different methods: DPPH free radical scavenging activity, ferrous ion chelating activity and reducing power activity. Finally, the antibacterial and antifungal activities of phthalocyanine compounds synthesized within the scope of this study were determined by disc diffusion and macrobroth dilution methods and the effect of the doping of Ag(i) and Pd(ii) ions on the antibacterial activities of phthalocyanines was investigated.

The use of water-soluble phthalocyanines as textile dyes in nylon/elastane fabric: fastness and antibacterial effectiveness.

This work reports on dyeing of nylon/elastane fabric with water-soluble phthalocyanines ( 1-4 ) bearing quinoline 5-sulfonic acid substituents on the peripheral or nonperipheral positions and determining the antibacterial efficiency of the phthalocyanine compounds and the dyed nylon/elastane fabrics. The light, washing, water, perspiration, and rubbing fastness properties of nylon/elastane fabrics dyed with phthalocyanines were also determined. The results showed that all dyed fabrics showed very good wet fastness values. The lightfastness value of the nylon/elastane fabric dyed with phthalocyanine dye ( 1 ) showed a much better value than the others. Also, the antibacterial efficiencies of the dyed nylon fabrics and the dye compounds were investigated against a gram-negative ( Escherichia coli ) and a grampositive ( Staphylococcus aureus ) bacteria by using disc diffusion method. The results showed that the dyed nylon/elastane fabrics and the compounds exhibited antibacterial activities against both bacteria.

Synthesis of non-peripherally tetra-substituted copper(ii) phthalocyanines: characterization, optical and surface properties, fabrication and photo-electrical properties of a photosensitive diode.

This study describes the synthesis and characterization of a non-peripherally tetra-substituted copper(ii) phthalocyanine bearing 4-(trifluoromethoxy)phenol groups. Some spectroscopic techniques such as FT-IR, 1H-NMR, 13C-NMR, MALDI-TOF, SEM and UV-vis were used to characterize the compounds. The novel molecule of 3-(4-(trifluoromethoxy) phenoxy) phthalonitrile (1) was confirmed and its molecular structure and supra-molecular dynamics were revealed by the analysis of single crystal X-ray diffraction measurements. Ligand (1) and its copper(ii) phthalocyanine (2) were theoretically examined via HF and B3LYP, M06-2X methods by using the 3-21G, 6-31G and sdd basis sets. The calculated values of IR, NMR and UV-Vis spectra for ligand (1) and its copper(ii) phthalocyanine (2) were compared with the experimentally obtained values. The absorbance and reflectance spectra, optical band gaps, refractive indices, and the optical and electrical conductivities of compound (2) for different concentrations were investigated in detail. We fabricated a photosensitive diode and investigated its photo-electrical properties under dark and light conditions.

Highly selective thioalcohol modified phthalocyanine sensors for Ag(I) and Pd(II) based on target induced J- and H-type aggregations: synthesis, electrochemistry and peripheral metal ion binding studies.

We have described highly selective 1(4),8(11),15(18),22(25)-(1-hydroxyhexan-3-ylthio)-phthalocyanine sensors, M{Pc[α-SCH(C(3)H(7))(C(2)H(5)OH)](4)} (MPc(α-HHT)(4), where M = Zn(II) (2), Cu(II) (3) or Co(II) (4) and HHT: -SCH(C(3)H(7))(C(2)H(5)OH)). The formation of S-M-S {S = sulfur; M = Ag(I) or Pd(II)} bonds on the periphery in the case of Ag(I) and Pd(II) metal ions induces H- or J-aggregation, respectively, which results in significant changes in the absorption of the B- and, in particular, the Q-band. The binding ratios of Ag(I) to the periphery of 2 and 3 were found to be ca. 2:1 and 3:2, respectively. On the other hand, the binding ratios of Pd(II) to the periphery of the same compounds were found to be 3:1 and 4:1. The fluorescence of 2 exhibited distinct changes in response to treatment with Ag(I) and Pd(II) ions in solution. The fluorescence spectra emission intensity of 2 was quenched upon titration with Ag(I) and Pd(II) and a new emission maximum was observed upon titration with Pd(II). FTIR, (1)H-NMR, (13)C-NMR, UV-vis, MALDI-TOF MS and elemental analysis data were used to characterize the novel compounds. Transmission electron microscopy (TEM) and field-emission scanning electron microscopy (FE-SEM) were also used as complementary techniques to investigate the morphology and to image the interfacial aggregates of 2. The redox behaviours of the complexes were examined by voltammetry and in situ spectroelectrochemistry on Pt in a nonaqueous medium.