Fluorinated Phthalocyanine/Silver Nanoconjugates for Multifunctional Biological Applications.

In this study, a new phthalonitrile derivative namely 4-[(2,4-difluorophenyl)ethynyl]phthalonitrile (1) and its metal phthalocyanines (2 and 3) were synthesized. The resultant compounds were conjugated to silver nanoparticles and characterized using transmission electron microscopy (TEM) images. The biological properties of compounds (1-3), their nanoconjugates (4-6), and silver nanoparticles (7) were examined for the first time in this study. The antioxidant activities of biological candidates (1-7) were studied by applying the 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging assay. The highest antioxidant activity was obtained 97.47 % for 200 mg/L manganese phthalocyanine-silver nanoconjugates (6). The antimicrobial and antimicrobial photodynamic therapy (APDT) activities of biological candidates (1-7) were examined using a micro-dilution assay. The highest MIC value was obtained 8 mg/L for nanoconjugate 6 against E. hirae. The studied compounds and their silver nanoconjugates exhibited high APDT activities against all the studied microorganisms. The most effective APDT activities were obtained 4 mg/L for nanoconjugates (5 and 6) against L. pneumophila and E. hirae, respectively. All the studied biological candidates displayed high cell viability inhibition activities against E. coli cell growth. The biofilm inhibition activities of the tested biological candidates were also investigated against S. aureus and P. Aeruginosa. Biological candidates (1-6) can be considered efficient metal nanoparticle-based materials for multi-disciplinary biological applications.

Effect of Axial Ligand Length on Biological and Anticancer Properties of Axially Disubstituted Silicon Phthalocyanines.

In this study, three new axially disubstituted silicon phthalocyanines (SiPc1-3) and their quaternized phthalocyanine derivatives (QSiPc1-3) were prepared and characterized. The biological properties (antioxidant, antimicrobial, antibiofilm, and microbial cell viability activities) of the water-soluble silicon phthalocyanines were examined, as well. A 1 % DMSO diluted with pure water was used as a solvent in biological activity studies. All the compounds exhibited high antioxidant activity. They displayed efficient antimicrobial and antimicrobial photodynamic therapeutic properties against various microorganisms, especially Gram (+) bacteria. Additionally, they demonstrated high antibiofilm activities against S. aureus and P. aeruginosa. In addition, 100 % bacterial reduction was obtained for all the studied phthalocyanines against E. coli viable cells. Besides, the DNA cleavage and binding features of compounds (QSiPc1-3) were studied using pBR322 DNA and CT-DNA, respectively. Furthermore, the human topoisomerase I enzyme inhibition activities of compounds QSiPc1-3 were studied. Anticancer properties of the water-soluble compounds were investigated using cell proliferation MTT assay. They exhibited anticarcinogenic activity against the human colon cancer cell line (DLD-1). Compounds QSiPc1 and QSiPc3 displayed a high anticarcinogenic effect on the DLD-1 cell line. The obtained results indicated that all the studied compounds may be effective biological agents and anticancer drugs after further investigations.

Electrodeposition of Manganese (III) Phthalocyanine/ Reduced Graphene Oxide for Asymmetric Supercapacitor Devices.

In this study, two novel tetra-substituted manganese (III) phthalocyanines bearing 9H-Carbazol-2-yloxy groups on peripheral or non-peripheral positions were prepared and used for modification of reduced graphene oxide by applying a simple one-step electrodeposition technique for the first time. The manganese (III) phthalocyanines (1 and 2) were electropolymerized and graphene oxide was electrochemically converted into reduced graphene oxide simultaneously. Subsequently, an rGO-MnPc hybrid structure was formed directly on the NiF electrode (substrate) via layer-by-layer assembly. Additionally, the effect of substituent position on the charge storage capacity of the prepared hybrid capacitive candidates was investigated. The fabricated hybrid electrodes exhibited remarkable electrochemical performance due to the combination of manganese (III) phthalocyanines and reduced graphene oxide. The NiF/rGO2-2 electrode exhibited the highest specific capacitance (512.4 F g-1) at 0.5 A g-1 and the remained specific capacitance was obtained 88.1% after 5000 consecutive charge-discharge cycles. An asymmetric supercapacitor (ASC) was constructed from rGO2-2 as the positive electrode and rGO as the negative electrode with a working potential of 1.5 V. The as-prepared device delivered a specific energy of 17.4 Wh kg-1 at 350 W kg-1. Hence, manganese (III) phthalocyanine-reduced graphene oxide electrodes can be considered outstanding materials for energy storage applications in the future.

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.

Supercapacitive properties of carbazole-containing cobalt(II) phthalocyanines/reduced graphene oxide composites.

This study aims to compare the effect of substituents (position and number) and reduced graphene oxide on the supercapacitive properties of cobalt(II) phthalocyanines. For this purpose, three new tetra- and octa-substituted cobalt(II) phthalocyanines bearing 9H-carbazol-2-yloxy groups on peripheral or non-peripheral positions (1-3) were synthesized. The characterization of the resultant cobalt(II) phthalocyanines was carried out by applying several spectroscopic approaches. The newly synthesized macromolecules were used for the functionalization of reduced graphene oxide (rGO). The obtained nanocomposites (rGO-(1-3)) were utilized for the modification of Ni foam (NiF) electrodes through a facile one-step electrodeposition strategy performed for electrochemical supercapacitor applications. Simultaneous polymerization of the cobalt phthalocyanines and electrochemically reduction of graphene oxide led to the formation of a fabricating layer on the surface of the NiF electrode. The resulting electropolymerized films were characterized by Raman, Fourier-transform infrared (FT-IR), and Field emission scanning electron microscope (FESEM) spectroscopic techniques as well as electrochemical methods. The prepared electrodes possessed superior electrochemical activities owing to the synergistic effect of the cobalt(II) phthalocyanines and rGO. All the modified electrodes displayed high supercapacitaive properties and the highest activity was obtained for the NiF/rGO2-1 electrode. The NiF/rGO2-1 electrode exhibited higher specific capacitance (655.2 F g-1 at 0.5 A g-1) than NiF/1 (338.0 F g-1). Additionally, a specific capacitance of 85.2% was obtained for NiF/rGO2-1 electrode after 3000 charge-discharge cycles. As a result, all the prepared metallophthalocyanines-reduced graphene oxide can be considered alternative agents to develop high performance-next-generation energy storage devices.

Design of N-heterocycle based-phthalonitrile/metal phthalocyanine-silver nanoconjugates for cancer therapies.

This study reports the anticancer properties of carbazole-containing phthalonitrile/phthalocyanine-modified silver nanoparticles for the first time. In this study, a new mono-substituted phthalonitrile namely 3-[9H-carbazole-9-ethoxy]phthalonitrile and its metal phthalocyanines {M = Zn, Co, and Mn(Cl)} were synthesized by template cyclotetramerization of phthalonitrile derivatives. The newly synthesized compounds were characterized using UV-vis, FT-IR, 1H NMR, 13C NMR, and mass spectroscopy. The resultant compounds were successfully linked to the surface of silver nanoparticles. The characterization of the surficial modification was carried out by applying the TEM technique. The cytotoxic activities of the studied nanoconjugates were tested against A549, DLD-1, and Wi38 cell lines by performing a (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) (MTT) assay with/without irradiation. Although the functionalization of silver nanoparticles increased the solubility of phthalocyanines in aqueous media, the presence of phthalonitrile/phthalocyanine derivatives on the silver nanoparticles' surface improved their biological properties. All the studied biological candidates exhibited antiproliferative activities against the cell lines. The IC50 values calculated were between 6.80 and 97.99 µM against the studied cell lines in the dark. However, the IC50 values determined were between 3.11 and 88.90 µM with irradiation. The highest IC50 values obtained were 3.11 and 3.52 µM against the DLD-1 cell line for nanoconjugates 1-AgNP and 3-AgNP, respectively. The findings indicated that the compounds may be utilized as anticancer agents after further studies.

Sonophotochemical and photochemical efficiency of thiazole-containing metal phthalocyanines and their gold nanoconjugates.

This study presents the synthesis of some metal {M = Zn(II), Lu(III), Si(IV)} phthalocyanines bearing chlorine and 2-(4-methylthiazol-5-yl) ethoxy groups at peripheral or axial positions. The newly synthesized metal phthalocyanines were characterized by applying FT-IR, 1H NMR, mass, and UV-Vis spectroscopic approaches. Additionally, the surface of gold nanoparticles was modified with zinc(II) and silicon(IV) phthalocyanines. The resultant nanoconjugates were characterized using TEM images. Moreover, the effect of metal ions and position of substituent, and gold nanoparticles on the photochemical and sonophotochemical properties of the studied phthalocyanines was investigated. The highest singlet oxygen quantum yield was obtained for the lutetium phthalocyanine by applying photochemical and sonophotochemical methods. However, the linkage of the zinc(II) and silicon(IV) phthalocyanines to the surface of gold nanoparticles improved significantly their singlet oxygen generation capacities.

New phthalonitrile/metal phthalocyanine-gold nanoparticle conjugates for biological applications.

The emergence of nanoscience and its effect on the development of diverse scientific fields, particularly materials chemistry, are well known today. In this study, a new di-substituted phthalonitrile derivative, namely 4,5-bis((4-(dimethylamino)phenyl)ethynyl)phthalonitrile (1), and its octa-substituted metal phthalocyanines {M = Co (2), Zn (3)} were prepared. All the newly synthesized compounds were characterized using a number of spectroscopic approaches, including FT-IR, mass, NMR, and UV-vis spectroscopy. The resultant compounds modified the surface of the gold nanoparticles (NG-1-3). Characterization of the newly synthesized conjugates was carried out by transmission electron microscopy. The antioxidant activity of compounds 1-3, NG-1-3, and NG was evaluated using the DPPH scavenging process and the highest radical scavenging activity was obtained with compounds 1, NG-1, 2, and NG-2 (100%). The antimicrobial activity of compounds 1-3, NG-1-3, and NG was studied using a microdilution assay and the most effective antimicrobial activity was obtained for NG-3 against all the tested microorganisms. The newly synthesized compounds demonstrated high DNA cleavage activity. Compounds 1-3, NG-1-3, and NG significantly inhibited the microbial cell viability of E. coli and exhibited perfect antimicrobial photodynamic therapeutic activity with 100% inhibition after 20 min LED irradiation. Besides, the biofilm inhibition activity of compounds 1-3, NG-1-3, and NG on the growth of S. aureus and P. aeruginosa were examined and compounds 1-3 and NG-1-3, especially NG-1-3, displayed high biofilm inhibition activities.

Anticancer and biological properties of new axially disubstituted silicon phthalocyanines.

This study reports the synthesis of three novel axially disubstituted silicon phthalocyanines (1-3-Si) and their quaternized phthalocyanines (1-3-QSi). The resulting compounds were characterized by applying spectroscopic techniques including 1H NMR, FT-IR, UV-vis, and mass spectroscopy. The biological properties of compounds 1-3-QSi, including DNA cleavage activities, DNA binding modes, and topoisomerase enzyme inhibition activities, were investigated using agarose gel electrophoresis. pBR322 plasmid DNA, CT-DNA, and AL-DNA (isolated from apricot leaf) were used for DNA studies. All the quaternized compounds exhibited acceptable DNA cleavage activities. Human topoisomerase I and E. coli topoisomerase enzymes were used for the topoisomerase I inhibition studies. All the quaternized complexes inhibited topoisomerase I activity. Moreover, these compounds were screened for cytotoxic and apoptotic effects against a human colon cancer cell line (DLD-1) by performing MTT and Annexin V assays. They exhibited toxicity and apoptotic effect on the DLD-1 cell line. The findings reveal that the compounds can be utilized for cancer therapy after further investigations.

Biological properties of hexadeca-substituted metal phthalocyanines bearing different functional groups.

In this study, a new tetra-substituted phthalonitrile (diethyl 2-(2-chloro-4,5-dicyano-3,6-bis(hexyloxy)phenyl)malonate) bearing three different substituents was synthesized and characterized. Due to the basic medium, transesterification occurred during the synthesis of the target phthalocyanines [M = Zn (II), Cu (II), Co (II), In (III), Lu (III)] in n-pentanol and the ethyl groups were replaced with pentyl groups. The biological features of the resultant compounds were studied for the first time in this study. All the compounds exhibited high antioxidant, antimicrobial, and DNA cleavage activities. The highest antioxidant activity was obtained 90.39% for lutetium phthalocyanine at 100 mg/L. The most effective MIC value was obtained 8 mg/L against Candida parapisilosis. The most effective microbial cell viability inhibition was obtained 100% for cobalt and lutetium phthalocyanines. They exhibited excellent biofilm inhibiton activities. Higher biofilm inhibition was achieved using light irradiation. The compounds exhibited higher biofilm inhibition activities with photodynamic against Staphylococcus aureus compared with Pseudo aureginosa.

Sensing alcohol vapours with novel unsymmetrically substituted metallophthalocyanines.

Unsymmetrically substituted phthalocyanines were synthesized by the well-known statistical condensation method using two differently substituted precursors, 4-tert-butylphthalonitrile and 4-(4-pyrrol-1-yl)phenoxyphthalonitrile. Spin-coated thin films of these compounds were subsequently exposed to varying concentrations of methanol, ethanol and butanol between 25 and 150 ppm in order to investigate the effects of the number of carbon atoms in the alcohol vapors. The results of this preliminary investigation indicated that sensor performance parameters such as sensitivity, response and recovery time strongly depend on the number of carbon atoms in the analyte molecules. It was found that the sensitivity of the sensors decreases with increasing number of carbon atoms. Electrochemistry studies of CoPc and MnClPc were carried out with cyclic and square wave voltammetry methods. Both complexes illustrated metal and ring-based electron transfer reactions. While CoPc underwent only one metal-based reduction ([CoIIPc2-]/[CoIPc2-]1-), two metal-based reductions ([Cl-MnIIIPc2-]/[Cl-MnIIPc2-]1- and [Cl-MnIIPc2-]1-/[Cl-MnIPc2-]2-) were observed with MnPc. Color changes during the in situ spectroelectrochemical measurements illustrated the versatility of the compounds for display technologies. Pyrrole-containing substituents of the complexes triggered their electropolymerization on the working electrode, which enhances their value as functional materials for modified electrodes.

Microwave-assisted synthesis of novel non-peripherally substituted metallophthalocyanines and their sensing behaviour for a broad range of Lewis bases.

The synthesis of novel, symmetrical, tetrasubstituted metallophthalocyanines (cobalt, zinc, and manganese) bearing four 2-(4-methyl-1,3-thiazol-5-yl)ethoxy units is reported. The new compounds have been characterized using UV-Vis, IR, (1)H NMR, (13)C NMR, and mass spectroscopy data. Photophysical properties of zinc(ii) phthalocyanines were found, including electronic absorption and fluorescence quantum yields. The fluorescence of the complexes was investigated in DMF and it was found that benzoquinone (BQ) was an effective quencher. The response and recovery behaviours of the spin coated films to different analytes, which span a broad range of Lewis bases, have been investigated by means of conductivity measurements. It was observed that the operating temperature had a considerable effect on the gas sensing performance of the sensors investigated. The sensing behaviour of the films for a broad range of Lewis bases and the correlation between the sensor sensitivity and Lewis base enthalpies were investigated. Results show that the sensitivity of the films may be correlated exponentially with the binding enthalpy.