Water-soluble Phthalocyanine Research Articles

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.

Photogeneration of Reactive Oxygen Species from Water-Soluble Phthalocyanine Derivatives Bound to a G-Quadruplex DNA

Abstract Water-soluble phthalocyanine (Pc) derivatives have been studied extensively as not only effective photosensitizers for photodynamic therapy (PDT), but also G-quadruplex ligands which have the potential to be anticancer drugs. We investigated the photogeneration of reactive oxygen species (ROS) from cationic Pc derivatives, 2,3,6,7,10,11,14,15-octakis-[N-methyl-(4-methylpyridinium-3-yloxy)phthalocyaninato] chloro gallium(III) iodide (GaPc) and zinc(II) iodide (ZnPc), in the presence of an all parallel-stranded tetrameric G-quadruplex DNA, i.e., [d(TTAGGGT)4]. We found that the photo ROS generation from GaPc is suppressed in the presence of the DNA, whereas that from ZnPc is enhanced on the addition of the DNA. The suppression of the photo ROS generation for GaPc by the DNA was found to be due to electron transfer from the ground state of the guanine base of the DNA to the photo-excited state of GaPc. This finding provides a clue as to why phototoxicity of GaPc is lower than that of ZnPc in human Hep2 cells (Fujishiro et al. J. Inorg. Biochem.2019, 192, 7). On the other hand, the enhancement of the photo ROS generation from ZnPc by the DNA is possibly due to the dissociation of its non-fluorescent aggregate through its interaction with the DNA. Thus the interaction of photosensitizers with DNA and RNA is crucial for their PDT efficacy.

Synthesis, characterization, photo-physicochemical and biological properties of water-soluble tetra-substituted phthalocyanines: 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.

Synthesis of water soluble tetra-substituted phthalocyanines: Investigation of DNA cleavage, cytotoxic effects and metabolic enzymes inhibition

In this study, we have reported the synthesis and characterization of 4-(sodium 2-mercaptoethane sulfonate) phthalonitrile (1) as ligand and its water-soluble phthalocyanine compounds [M = 2H (2), Zn(II) (3), Ga(III)Cl (4), In(III)Cl (5)] containing sodium 2-mercaptoethanesulfonate substituents at the peripheral positions. All compounds were characterized by UV–Vis, FT-IR and NMR spectroscopies, and MALDI-TOF mass spectra. Besides, the DNA cleavage effects of the phthalocyanine compounds were investigated using agarose gel electrophoresis and cytotoxic effects of them were determined on BT-20, DU-145, A549, SNU-398 and HFC cell lines using MTT assay. The compounds cleaved supercoiled pBR322 plasmid DNA upon irradiation (white, 17.5 mW/cm2, 60 min) in the presence of H2O2. The IC50 values of (2) were determined as 145.76, 93.75, 124.73, 128.81 and 136 μM on BT-20, DU-145, A549, SNU-398 and HFC cell lines, respectively. The IC50 values of others were above 200 μM on five cell lines. These results showed that the compounds had low cytotoxic effects against breast, prostate, lung and liver cell lines. These water-soluble phthalocyanine compounds [M = 2H (2), Zn(II) (3), Ga(III)Cl (4), In(III)Cl (5)] were found to be good inhibitor against the α-glycosidase, human carbonic anhydrase I and II isoforms, and both cholinesterase enzymes with Ki values in the range of 84.02 ± 16.95–166.47 ± 14.87 μM for α-glycosidase, 7.54 ± 1.02–31.65 ± 3.08 μM for hCA I, 5.97 ± 0.97–36.13 ± 6.97 μM for hCA II, 1.02 ± 0.14–3.42 ± 0.86 μM for BChE, and 2.01 ± 0.32–3.98 ± 0.12 μM for AChE, respectively.

Light driven photodegradation of 4-nitrophenol with novel Co and Cu phthalocyanine in aqueous media

In this work, we have used two different metal centered water soluble phthalocyanines for the degradation of 4-nitrophenol in water media. In the photodegradation reactions that took place in the photoreactor for 1 h without using any oxidant, 4-nitrophenol compound was completed with 95% (for CoPc) and 97% (for CuPc) conversion to toxic and non-harmful species. The hydroquinone compound was identified as the main product and the benzoquinone compound as the by-product. The turnover number for Cu phthalocyanine was 1896 and for Co phthalocyanine was 2101. Finally, recovery studies were carried out for water soluble Cu phthalocyanine used as photocatalyst and the number of cycles was determined as 7.

Supramolecular Phthalocyanine Assemblies for Improved Photoacoustic Imaging and Photothermal Therapy

Phototheranostic nanoplatforms are of particular interest for cancer diagnosis and imaging-guided therapy. Herein, we develop a supramolecular approach to fabricate a nanostructured phototheranostic agent through the direct self-assembly of two water-soluble phthalocyanine derivatives, PcS4 and PcN4. The nature of the molecular recognition between PcS4 and PcN4 facilitates the formation of nanostructure (PcS4-PcN4) and consequently enables the fabrication of PcS4-PcN4 with completely quenched fluorescence and reduced singlet oxygen generation, leading to the high photoacoustic and photothermal activity of PcS4-PcN4. In vivo evaluations suggest that PcS4-PcN4 could not only efficiently visualize a tumor with high contrast through whole-body photoacoustic imaging but also enable excellent photothermal therapy for cancer.

Photo-physicochemical properties of water-soluble non-aggregated indium(III) phthalocyanines.

Phthalocyanines have interesting optoelectronic properties but typically suffer from aggregation in aqueous solution, which can limit their applicability, especially in photodynamic therapy. In this study, indium(III) phthalocyanine peripherally substituted with eight triazolyl-containing phenoxy groups (InOAc) and its water-soluble analogue (Q-InOAc) were synthesised and structurally characterised. Heavy metal effects, exerted by the central indium ion, on the photosensitising and photophysical properties (singlet oxygen quantum yield, singlet state lifetime and quantum yield, and triplet state lifetime) were investigated in both DMF and D2O. Highly efficient generation of the triplet excited state (T1), induced by the incorporation of a large atom, enhanced singlet oxygen formation, as revealed by both chemical and physical methods. Correspondingly, the singlet oxygen quantum yield (ΦΔ) of Q-InOAc was 0.603 in DMF and 0.433 in D2O. These values are higher than those previously reported for the corresponding metal-free, Mg-based, and Zn-based water-soluble phthalocyanines (HH, Mg, and Zn). Consequently, Q-InOAc is expected to be an excellent photosensitiser for photodynamic therapy.

Exfoliation inhibition on aluminum alloy 7075 by water-soluble phthalocyanine derivates in 1 mol/L HCl

The inhibition effects of two phthalocyanine sulfonates on aluminum alloy 7075 were investigated in this study. The gravimetric test showed that the two compounds effectively inhibited the exfoliation corrosion of aluminum alloy 7075 in 1 mol/L hydrochloric acid. The electrochemical test showed the phthalocyanine sulfonates mainly acted as mixed-type inhibitors. The molecular dynamic simulation indicated that the phthalocyanine inhibitors selectively adsorbed on aluminum atoms, which inhibited the dealloying of aluminum from the alloy surface. In XPS analysis, the chemical adsorption between aluminum and phthalocyanine inhibitors was proven by the changes in the electronic binding energy of Al and N.

Synthesis, characterization and staining performance of peripherally and non-peripherally substituted metallo-phthalocyanines bearing 1,3-bis-(trimethylamino)-2-propoxy groups

In this study, water-soluble symmetrical phthalocyanines having cationic 1,3-bis-(trimethylamino)-2-propoxy groups at the peripheral and non-peripheral positions were synthesized and characterized.

Antioxidant properties of water-soluble phthalocyanines containing quinoline5-sulfonic acid groups

In the present study, the antioxidant properties of peripherally and nonperipherally water-soluble tetra (quinoline 5-sulfonic acid) substituted metal-free (1,2), Zn(II) (3, 4), Co(II) (5, 6), and Mn(III)Cl (7, 8) phthalocyanine (Pc) derivatives were reported. In order to determine the antioxidant properties of the Pc compounds, three different commonly known antioxidant methods were used: DPPH ($\alpha $,$\alpha $-diphenyl-$\beta $-picrylhydrazyl) radical scavenging, ferrous ion chelating, and reducing power assays. Compound \textbf{6} showed the best DPPH activity among the other tested compounds except for the standards. The ferrous ion chelating IC$_{50\, }$value of compound 7 was nearly as good as that of the EDTA standard. The reducing power activity results indicated that the tested Pc compounds were as sensitive as standard reducing agents such as butylated hydroxytoluene and ascorbic acid. Overall, all tested compounds showed good antioxidant properties and it may be suggested that they could be used as new positive controls for reducing power assays in the future works.

Synthesis and physicochemical properties of organo- and water-soluble octasubstituted phthalocyanines with cyclohexylphenoxy groups

Synthesis of 4-(4-cyclohexylphenoxy)-5-nitrophthalonitrile was developed. The method was used for the synthesis of cobalt, zinc, and copper tetra-4-(4-cyclohexylphenoxy)tetra-5-nitrophthalocyanines and their water-soluble analogs.

Novel water soluble 7-oxy-4-(pyridine-3-yl)coumarin substituted phthalocyanines as potential photosensitizers for photodynamic therapy

The new phthalonitriles (1 and 2) and zinc, indium, magnesium metalled tetrasubstituted phthalocyanines bearing 7-oxy-4-(pyridine-3-yl)coumarin substituents in the peripheral (1a-c)/non-peripheral (2a-c) positions were prepared for the develop novel water-soluble phthalocyanines. Newly synthesized phthalocyanines were turned into highly water-soluble quaternized ionic counterparts (1d-f, 2d-f). The effects of metal ions and substituents in the phthalocyanine ring on spectral, photochemical and photophysical properties of newly prepared phthalocyanines were examined of the non-ionic phthalocyanines (1a-c, 2a-c) in DMF and quaternized ionic phthalocyanines (1d-f, 2d-f) in both of DMF and water. Water-soluble peripheral substituted indium (III) (1e) and non-peripherally substituted zinc (II) (2d), indium (III) (2e) phthalocyanines showed good singlet oxygen formation that performed them as a highly promising photosensitizers for photodynamic therapies.

Post‐modification of phthalocyanines via isocyanide-based multicomponent reactions: Highly dispersible peptidomimetic metallophthalocyanines as potent photosensitizers

In this work, one-step synthesis of highly dispersible phthalocyanines containing carboxamide moieties via four-component Ugi reaction was demonstrated for the first time. These pseudopeptide-modified-phthalocyanines were characterized by means of IR, NMR, CHN and UV–Vis spectroscopy. Additionally, the purity of the pseudopeptide phthalocyanines was confirmed by capillary zone electrophoresis. Most of the synthesized phthalocyanines showed good dispersity in common organic solvents and especially in water. The in vitro photodynamic activities of water-soluble phthalocyanine 5k upon MCF-7 cancer cells were investigated and revealed that the cell viability was high in dark conditions, while the compound was phototoxic at visible light and the intensity of damage was directly related to its concentration. Also, phthalocyanine 5k showed high cellular uptake and more killing cells after the modification with Ugi-4CR. Since, many potent phthalocyanine photosensitizers are hydrophobic and poorly water-soluble, which limit their therapeutic applications, the novel phthalocyanines which modified through Ugi approach could be introduced as potent hydrophilic, nonaggregated and biocompatible sensitizers which can able to improve the effectiveness of photodynamic therapy.

Water-Soluble Phthalocyanines Selectively Bind to Albumin Dimers: A Green Approach Toward Enhancing Tumor-Targeted Photodynamic Therapy.

Targeted delivery of therapeutic agents is of particular interest in the field of cancer treatment. However, there is an urgent need for developing clinically promising targeting approaches that can be readily administered in a green manner.Methods: Five phthalocyanine derivatives bearing different anionic and cationic groups were designed and synthesized. Then, their binding affinity with albumin were studied using gel assays, optical spectra and computational simulation. Finally, in vitro and in vivo fluorescence imaging and photodynamic therapy (PDT) evaluations were carried out.Results: The two positively charged compounds could selectively bind to albumin dimer over albumin monomer, while the three negatively charged phthalocyanines could bind to both albumin monomer and dimer. Following systemic administration, the phthalocyanines show improved tumor accumulation via transport by natural albumin. PDT evaluations indicate that one of the positively charged compounds, ZnPcN4, shows outstanding phototherapeutic efficacy against tumors in preclinical models.Conclusion: Our findings demonstrate that the use of water-soluble phthalocyanines as photosensitizers and in vivo albumin as a natural carrier may provide a green and efficient approach for tumor-targeted imaging and therapy.

Non-aggregated zwitterionic Zinc(II) phthalocyanine complexes in water with high singlet oxygen quantum yield

Syntheses of non-peripheral (4) and peripheral (5) 2-(4-methyl-1,3-thiazol-5-yl)ethanol substituted zinc (II) phthalocyanines were achieved in this study. These zinc(II) phthalocyanines were converted to their quaternized ionic (4a and 5a) and zwitterionic (4b and 5b) derivatives. The structures of these novel compounds were characterized by elemental analysis and different spectroscopic methods such as FT-IR, UV-Vis, NMR and mass. General trends were examined for aggregation behaviours, photochemical and photophysical properties of the non-ionic zinc (II) phthalocyanines (4 and 5) in DMSO and their water soluble cationic (4a and 5a) and zwitterionic (4b and 5b) derivatives in both of DMSO and phosphate solution (PBS). The effect of different position and quaternization or zwitterionization of the binding groups on the photophysical and photochemical properties were also announced. Water soluble zwitterionic compound 4b exhibited very high singlet oxygen generation which makes it ideal photosensitizer in treatment of cancer by photodynamic therapy method. The fluorescence of the tetra-substituted zinc (II) phthalocyanines (4 and 5) are effectively quenched by addition of 1,4-benzoquinone (BQ). Furthermore, the water soluble phthalocyanine derivatives (4a, 5a, 4b and 5b) can bind to bovine serum albumin (BSA) which is a blood plasma protein.

Phthalocyanine-Sensitized Generation of Silver Nanoparticles in Aqueous Buffer Solution Triggered by Red LED-Light.

Silver nanoparticles have been generated in aqueous buffer solution using a water-soluble silicon phthalocyanine sensitizer. Red light illumination (660 nm LED) was performed under aerobic conditions at ambient temperature in the presence of TEOA as a reductant. Structural characterization of the Ag nanoparticles formed was carried out by transmission electron microscopy (TEM). The resulting silver particles, depending on irradiation time and choice of procedure, were found to have a spheric shape and a narrow size distribution of 5-10 nm.

Solvent effects on molecular aggregation of highly water-soluble phthalocyanines

Molecular aggregation phenomena of a highly water-soluble, metal-free phthalocyanine, H[Formula: see text]Pc, and its copper complex, Cu(Pc); where Pc denotes tetrakis{(2[Formula: see text],6[Formula: see text]-dimethyl-4[Formula: see text]-sulfonic acid)phenoxy}phthalocyaninate) in water, ethanol, and their mixed solvent systems have been investigated by spectroscopic approach In both aqueous and ethanolic solutions, H[Formula: see text]Pc molecules aggregate in a slipped-cofacial manner, although very weakly in ethanol. On the other hand, Cu(Pc) molecules aggregate in a cofacial manner in water while aligning in a slipped-cofacial manner in ethanol. Magnetic circular dichroism spectroscopy was undertaken to investigate aggregation behaviors of Cu(Pc) in water and ethanol. Presence of 4-phenylpyridine in ethanol effectively inhibited aggregation of Cu(Pc) molecules, although little affected the spectra of the monomers. In a mixed solvent system, where water/ethanol [Formula: see text] 10/90 (v/v), Cu(Pc) is free from aggregation up to almost 10[Formula: see text] M. Driving forces of this molecular aggregation are discussed on the basis of [Formula: see text]–[Formula: see text] interaction and coordination chemistry involving copper ions.

Synthesis of Water-Soluble Phthalocyanines and Modification of their Peripheral Fragments as a Method of Directed Changes in Lipophilic-Hydrophilic Properties

This article brief by describes results of studies devoted to synthesis of water-soluble phthalocyanines derivatives, which are carried out by the Complexing Agents Chemistry group of IPAC RAS. Metal-free ligands and metallophthalocyanines, containing peripheral substituents with fragments of pyridine, oxybenzoic and hydroxyphenylphosphonic acids are potential photosensitizers for photodynamic therapy of cancer diseases. Methods for the modification of peripheral substituents have been developed that make it possible to synthesize phthalocyanine ligands and complexes soluble in organic solvents, or soluble in aqueous media and also possess amphiphilic properties.

Photophysicochemical, calf thymus DNA binding and in vitro photocytotoxicity properties of tetra-morpholinoethoxy-substituted phthalocyanines and their water-soluble quaternized derivatives.

In this study, morpholinoethoxy-substituted metal-free (3), zinc(II) (4) and indium(III) (5) phthalocyanines were synthesized. These phthalocyanines were converted to their water-soluble quaternized derivatives (3Q-5Q) using excess methyl iodide as a quaternization agent. All these phthalocyanines (Pcs) were characterized by elemental analysis and different spectroscopic methods such as FT-IR, 1H NMR, UV-Vis and mass spectrometry. The photophysical and photochemical properties such as fluorescence and generation of singlet oxygen were investigated for determination of these phthalocyanines as photosensitizers in photodynamic therapy (PDT) applications. The binding properties of quaternized phthalocyanines (3Q-5Q) to calf thymus DNA (CT-DNA) were investigated by UV-Vis and fluorescence spectrophotometric methods. The quenching effect of all quaternized phthalocyanines on the fluorescence intensity of SYBR Green-DNA complex was determined. The mixtures of 3Q, 4Q or 5Q and DNA solutions were used to determine the change in T m of double helix DNA with thermal denaturation profile. In addition, thermodynamic parameters considering their aggregation in buffer solution, which shows the spontaneity of the reactions between DNA and quaternized Pcs were investigated. On the other hand, in vitro phototoxicity and cytotoxicity behavior of the quaternized water-soluble phthalocyanine photosensitizers (3Q-5Q) were tested against the cervical cancer cell line named HeLa for evaluation of their suitability for treatment of cancer by PDT method. Peripherally tetra-substituted neutral and quaternized metal-free and metallophthalocyanines (MPcs) (Zn, In) bearing morpholinoethoxy groups were prepared. The binding of quaternized compounds (3Q-5Q) to CT-DNA were examined using UV-Vis, fluorescence spectra, thermal denaturation profiles and K SV values. Besides, thermodynamic studies indicated that binding of 3Q-5Q to DNA was spontaneous. On the other hand, in vitro phototoxicity and cytotoxicity behavior of the quaternized water-soluble phthalocyanine photosensitizers (3Q-5Q) were tested against the cervical cancer cell line named HeLa for evaluation of their suitability for treatment of cancer by PDT method.

Effect of New Water-Soluble Dendritic Phthalocyanines on Human Colorectal and Liver Cancer Cell Lines

Human hepatocellular carcinoma (HepG2) cells and colorectal adenocarcinoma (DLD-1) cells were treated with the synthesized water soluble phthalocyanine derivatives to understand the effect of the compounds both on colorectal and liver cancer cells. The compounds inhibited cell proliferation and displayed cytotoxic effect on these cancer cell lines however; the effect of the compounds on healthy control fibroblast cell line was comparatively lower. The compounds can be employed for cancer treatment as anticancer agents.