Soluble Phthalocyanine Research Articles

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.

Thermally stable dopant-free soluble phthalocyanines as hole transporting materials for Perovskite solar cells

In enhancing the durability and photovoltaic performance of Perovskite solar cells, Hole transport Materials (HTMs) play the key role. In search of new HTMs, in this work, we have designed, synthesized and characterized 3,4,5 trimethoxy phenoxy substituent free-base soluble phthalocyanine (H2-TmPc) along with their metallo derivates with Cu(II) (Cu-TmPc) and Zn(II) (Zn-TmPc) derivatives and applied them as HTMs for PSC. All three HTMs were characterized by optical, electrochemical, thermal and impedance studies. Absorption spectra in chlorobenzene revealed two Q bands and a soret band whereas metallo derivatives showed a single Q and soret band. Electrochemical studies revealed that these HTMs are capable of extracting holes from the Perovskite layer. Impedance studies showed that Cu-TmPc showed high specific conductance of 1.78× 10[Formula: see text] when compared to other derivatives. Based on these data PSCs were fabricated with these Pc series as HTMs and SnO2 as ETL layer and noticed that Cu-TmPc gave a power conversion efficiency of 5.7%.

An investigation on photocatalytic and α-amylase inhibitory activities of Co(II) and Zn(II) phthalocyanines

Metallophthalocyanines have broad range of photocatalytic and biological applications, so they have been investigated widely by the scientific community. In this study, P4P-1 and P4P-2 phthalocyanines and their water soluble derivatives (QP4P-1 and QP4P-2) were synthesized and characterized by different spectral data. Photocatalytic performance of QP4P-1 and QP4P-2 were tested on photodegradation of 4-nitrophenol (4-NP). QP4P-1 shows remarkable photocatalytic activity with 90 % product conversion (TON:1500) in aqueous solution of 4-nitrophenol. α-amylase inhibition assay is performed in order to find out the enzyme inhibitory potential of water soluble phthalocyanine QP4P-2. QP4P-2 inhibited α-amylase 64.2 ± 0.8 % at 300 µM concentration and the IC50values ​​of the molecule was calculated as 128.2 ± 1.5 µM. QP4P-2 reflects the potential α-amylase inhibitory activity as compared to others.

C64 Nanographene Tetraimide—A Receptor for Phthalocyanines with Subnanomolar Affinity

AbstractPhthalocyanines are extensively used by the dye and pigment industry and in photovoltaic and photodynamic therapy research due to their intense absorption of visible light, outstanding stability, and versatility. As pigments, the unsubstituted phthalocyanines are insoluble owing to strong intermolecular π‐π‐stacking interactions, which causes limitations for the solution chemistry for both free base and metalated phthalocyanines. Here we show a supramolecular host–guest strategy to dissolve phthalocyanines into solution. C64 nanographene tetraimide (1) binds two free base/zinc/copper phthalocyanines in a 1 : 2 stoichiometry to solubilize phthalocyanines as evidenced by 1H NMR spectroscopy, UV/Vis absorption and single‐crystal X‐ray analysis. Binding studies using a tetra‐tert‐butyl‐substituted soluble phthalocyanine revealed binding affinities of up to 109 M−1 in tetrachloromethane, relating to a Gibbs free energy of −52 kJ mol−1. Energy decomposition analysis revealed that complexes between 1 and phthalocyanines are stabilized by dispersion interactions followed by electrostatics as well as significant charge‐transfer interactions.

C64 Nanographene Tetraimide - a Receptor for Phthalocyanines with Subnanomolar Affinity.

Phthalocyanines are extensively used by the dye and pigment industry and in photovoltaic and photodynamic therapy research due to their intense absorption of visible light, outstanding stability and versatility. As pigments, the unsubstituted phthalocyanines are insoluble owing to strong intermolecular π-π-stacking interactions which causes limitations for solution chemistry for both free base and metalated phthalocyanines. Here we show a supramolecular host-guest strategy to dissolve phthalocyanines into solution. C64 nanographene tetraimide (1) binds two free base/zinc/copper phthalocyanines in a 1:2 stoichiometry to solubilize phthalocyanines as evidenced by 1H NMR, UV-Vis absorption and single crystal X-ray analysis. Binding studies using a tetra-tert-butyl substituted soluble phthalocyanine revealed binding affinities of up to 109 M-1 in tetrachloromethane, relating to a Gibbs free energy of - 52 kJmol-1. Energy decomposition analysis revealed that complexes between 1 and phthalocyanines are stabilized by dispersion interactions followed by electrostatics as well as significant charge-transfer interactions.

Interaction of water soluble phthalocyanine compounds with parallel and hybrid G-quadruplex DNA molecules

G-quadruplex DNAs are secondary DNA structures formed in guanine-rich genome sequences, such as telomeres. Due to the increased metabolic activities of cancer cells, the formation probability of G-quadruplex structures increases. Since the formation of G-quadruplex structures and their stabilization with various ligands prevents DNA’s turning into straight strands, which are necessary for some processes such as transcription and translation, it may cause disruptions in cell proliferation. Therefore, these DNA constructs are important for anticancer drug targets. In the present study, the interactions of water-soluble MnPc and ZnPc compounds with G-quadruplex DNAs with parallel and hybrid conformation were investigated. KD constants were calculated with spectroscopic titration data. Stoichiometric ratios of DNA-phthalocyanine interactions were determined by Job’s method and found between 1:1 to 1:2 for MnPc and 1:1 for ZnPc. The effect of phthalocyanine on the G-quadruplex conformation was investigated by circular dichroism (CD) spectroscopy. Capillary gel electrophoresis studies supported the existence of interactions. DNA polymerase stop assay further supported stabilizing AS1411 and Tel21 G-quadruplex structures with Pc compounds. This work is on a molecular level study. The in vitro and in vivo images can be different because MPcs are localized in the cytoplasmic organelles but rare in the nucleus.

Electrochemical, spectroelectrochemical, and electrocatalytic properties of novel soluble phthalocyanines containing peripheral thymoxy and chloride units

Novel CoPc, CuPc, Fe(OAc)Pc and Mn(Cl)Pc were synthesized by using original 4-chloro-5-(2-isopropyl-5-methylphenoxy)phthalonitrile in order to investigate their potential redox applications suitable with their chemical and physical characteristics. The molecular structures of new compounds were determined with spectroscopic methods such as elemental analysis, FT-IR, UV–vis, NMR and MALDI TOF MS. Redox behaviours of Fe(OAc)Pc and Mn(Cl)Pc complexes have been probed by using diverse voltammetric techniques such as cyclic (CV) and square wave voltammetry (SWV). In addition, the colour alterations accompanying spectral changes were perused concurrently with electrocolorimetric measurements, and electrocatalytic efficiencies of the all compounds were perused in oxygen reduction reaction.

Solution-based fullerene-free route enables high-performance green-selective organic photodetectors

Ongoing developments in machine vision, wearables, and the Internet of Things have led to strong demand for easy-to-fabricate, color-selective photodetectors. Narrowband-absorption-type (NBA) printable organic photodetectors provide an attractive solution, given their spectral robustness and fabrication simplicity. However, a key remaining challenge to realizing their potential is to concurrently achieve high photoconversion efficiency and spectral selectivity. Herein, this challenge is tackled by investigating a non-fullerene-based route to green-selective, solution-based photodetectors. Soluble phthalocyanine acceptor PhO-Cl6BsubPc is considered due to its high absorption selectivity to green photons. Blends with soluble quinacridones are pursued to realize the ideal of a donor:acceptor layer selectively absorbing the target photons throughout its volume. A latent-pigment route to the solution-based deposition of linear trans-quinacridone (QA) enables well-intermixed QA:PhO-Cl6BsubPc layers. Green-selective photodetectors with cutting-edge performance are thus realized, achieving a 25% increase in external quantum efficiency compared to all prior solution-based NBA implementations, as well as a nearly five-fold enhancement of the green-to-blue spectral rejection ratio. The merit of this approach is further illustrated by comparison with the corresponding fullerene-based photodetectors. By demonstrating an approach to solution-based NBA photodetectors with cutting-edge photoconversion efficiency and spectral selectivity, this study represents an important step toward printable, high-performance organic color sensors and imagers.

Synthesis of water soluble copper(II), manganese(III) phthalocyanines and their photocatalytic performances in benzyl alcohol photoxidation

In this study, peripherally tetra-{[4-(3,5-dichlorophenyl)-5-pyridin-4-yl-4H-1,2,4-triazol-3-yl]thio} group substituted cobalt(II), manganese(III) phthalocyanines (BS-1-Cu, BS-1-Mn) and their water soluble derivatives (BS-1-CuQ, BS-1-MnQ) were synthesized via multistep reactions. The structure of new compounds were characterized by FT-IR, 1H-NMR, 13-CNMR, Mass, and UV visible spectroscopy. Then, photocatalytic properties of water soluble phthalocyanines (BS-1-CuQ, BS-1-MnQ) were investigated in benzyl alcohol (BA) photoxidation reaction. Photocatalytic results indicate that the former has high benzaldehyde selectivity (93%) and the latter employees with high product conversion (83%) at the same reaction conditions. The same yield of benzaldehyde (59%) was calculated with both photocatalysts at room temperature in water. The photocatalytic activity of BS-1-CuQ and BS-1-MnQ was evaluated by changing substrate amount and oxidant type. Additionally, the degradation of the BA were investigated in the presence of 0.05 g catalyst, 100 ml 0.015 M BA solution, 25 °C, 15 min in water. The recycling studies indicated that BS-1-MnQ can be used after 4 cycles, BS-1-CuQ can be used even after 3 cycles.

Non-canonical anti-cancer, anti-metastatic, anti-angiogenic and immunomodulatory PDT potentials of water soluble phthalocyanine derivatives with imidazole groups and their intracellular mechanism of action

Cancer is currently a leading health issue globally. Chemotherapy is a prominent treatment method but due to undesired side effects t, there has been a need for novel less toxic approaches. Photodynamic therapy may be listed among the alternatives for efficient and potentially less detrimental applications of cancer therapy. Canonical photodynamic therapy (PDT) approach requires a light source with a specific wavelength of light, a non-toxic photosensitizer and molecular oxygen. PDT creates the desired effect by the photochemical reaction created through interaction of these components to create reactive oxygen species that will act on the cancer cells to enable anti-cancer activities. In our study we focus on non-canonical PDT application. In this approach we are not only aiming to eliminate cancer cells in the environment but also test the anti-metastatic, anti-angiogenic and possible immunomodulatory activities of the novel photosensitizers. Moreover, in our approach, we studied the intracellular pathways that are crucial for carcinogenesis, cell cycle, apoptosis, angiogenesis, metastasis and immune function to decipher the mechanism of the action for each compound. Reactive oxygen species based explanation was not valid in our study, hence it brings out a non canonical approach to PDT applications. Our results suggests that Phthalocyanine derivatives with imidazole groups can be effectively used against lung, colon, breast and prostate cancer while differentially effecting metastasis, angiogenesis, cell cycle, apoptosis and immune system cells’ activities. Based on the results, PDT application of these phthalocyanine derivatives can be an effective treatment option to replace chemotherapy to minimize the potential side effects.

Synthesis and QCM gas-sensing properties of 3,4-dialkoxyphenyl tosylamino-substituted phthalocyanines

Octa-substituted metallophthalocyanines [M = Ni(II), Zn(II), Co(II), and Cu(II)] carrying 3,4-dialkoxyphenyl tosylamino groups at the peripheral positions have been synthesized from 1,2-dicyano-4,5-bis[(3,4-dialkoxyphenyl-tosylamino)methyl]benzene in the presence of the corresponding anhydrous metal salt. Next to the metal ion center, the length of the alkyl chains in the dialkoxyphenyl moiety ([Formula: see text], 5, 6, and 12) was varied. In total, sixteen soluble phthalocyanines have been characterized by elemental analysis, FT-IR and [Formula: see text]H-NMR spectroscopy as well as mass spectrometry. Furthermore, the gas sensing properties of these new compounds have been studied using quartz crystal microbalance transducers. The sensing properties are described on the basis of sensor responses to nine different test analytes comprising volatile organic compounds, toxic gases, and chemical warfare agent simulants. The influence of the metal ion center and substituents on sensor selectivity and sensitivity is discussed. The compounds show good performance in the gas-sensing experiments with diverse responses to the analytes. Phthalocyanine species with pronounced selectivity for polar analytes, hydrocarbons or amines have been identified among the set of sensors with the help of multivariate data exploration methods. The results reveal that quite a high diversity in terms of selectivity is introduced through the minute variations to the phthalocyanine structure.

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.

Synthesis and property study of phthalocyanine tetraimides as solution processable electron acceptors

Soluble phthalocyanine tetraimides (PcTIs) with hydrophobic side chains were designed and synthesized via three routes. Their absorption, fluorescence, electrochemistry, stability, charge mobility, and geometries were investigated. These planar conjugation compounds with intense absorption in 550–850 nm, deep lowest unoccupied molecular orbitals of −3.92 to −3.98 eV, decomposition temperature higher than 400 °C, and highest electron mobility of 4.88 × 10−4 cm2 V−1 s−1 (SCLC) were excellent solution processable acceptors. Bulk heterojunction solar cells based on acceptor CuPcTI-C11 reached a power conversion efficiency of 1.17% which is the highest value among phthalocyanine derivatives.

The Oxidation of 4-(4-Formylphenoxy) Phthalonitrile to 4-(4-Carboxylphenoxy) Phthalonitrile at Ambient Conditions

The substituted phthalonitriles have been used to prepare soluble phthalocyanine species in recent years. One of the most used phthalonitrile derivatives for the target product is 4-nitrophthalonitrile. In this study 4-(4-formylphenoxy) phthalonitrile was prepared as the substituted phthalonitrile derivative by the nucleophilic substitution reaction of para-hydroxybenzaldehyde with 4-nitrophthalonitrile. During the crystallization of the product by slow evaporation technique, it readily self-oxidized to 4-(4-carboxylphenoxy) phthalonitrile at ambient condition open to air. The crystal structure of the molecule was determined by XRD technique. The molecule crystalizes at triclinic space group P-1 and the unit cell parameters of crystal are a=6.3591 (10) Å, b=7.5464 (11) Å, c=13.819 (2) Å, α=88.434 (11)°, β=87.942 (12)°, γ=80.111 (12)° and Z=2. The crystal structure has intermolecular O―H∙∙∙O, C―H∙∙∙N and C―H∙∙∙O hydrogen bonds. In addition to these hydrogen bonds, C—N∙∙∙Cg and Cg∙∙∙Cg interactions are present between molecules. In the crystal, intermolecular O―H∙∙∙O hydrogen bonds occur between molecular units in a dimeric molecular form. Molecular structure, vibrational frequencies and 1H and 13C NMR chemical shifts of the target compound have been calculated by using B3LYP method with 6-311++G(d, p) basis set, as well.

Synthesis and catalytic performance of a soluble asymmetric zinc phthalocyanine

The soluble asymmetric phthalocyanine (Pc) (ZnPc-OH) was synthesized and used as a photosensitizer to degrade water pollutants. The catalytic ability of zinc Pc was proved by degrading Rhodamine B. In addition, ZnPc-OH, which has good solubility, can be used in photodynamic therapy.

Ethylene and Cyclohexene Oxidation by p-Benzoquinone, Hydrogen Peroxide, and Oxygen in the Solutions of Cationic Pd(II) Complexes in Acetonitrile–Water and Ionic Liquid–Water Binary Solvents

Optimal conditions are selected for ethylene and cyclohexene oxidation reactions in the acetonitrile (AN)–water system in the presence of $${\text{Pd}}{{({\text{AN}})}_{x}}({{{\text{H}}}_{2}}{\text{O}})_{{4 - x}}^{{2 + }}$$ complexes. It is shown that hydrogen peroxide oxidizes hydroquinone (QН2) in acetonitrile solutions and in ionic liquids ( $${\text{BMI}}{{{\text{M}}}^{ + }}{\text{BF}}_{4}^{ - },$$ $${\text{BMI}}{{{\text{M}}}^{ + }}{\text{PF}}_{6}^{ - }$$ ), and the rates of ethylene oxidation in the $${\text{BMI}}{{{\text{M}}}^{ + }}{\text{PF}}_{6}^{ - }$$ ionic liquid in the presence of p-benzoquinone (Q) and hydroquinone are the same. It is shown that solid and soluble phthalocyanine iron complexes catalyze oxidation of olefins by oxygen in acidic acetonitrile media by converting p-benzoquinone to the third catalyst of the process. The apparent first-order rate constants of hydroquinone oxidation by oxygen are determined. The use of the IL–Н2О–Н2SO4 system is found to be inappropriate for cyclohexanone synthesis because of the formation of byproducts of cyclohexene conversion.

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.

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.

Preparation of Cobalt Phthalocyanine Supported Mg-Al Hydrotalcite and its Catalytic Activity for Degradation of Methylene Blue

A novel supported catalyst is prepared through immobilization of water soluble phthalocyanine, which is synthesized by modifying tetraminophthalocyanine with cyanuric chloride, onto the supporting material Mg-Al hydrotalcite via co-precipitation method. The structure of the catalyst is characterized by infrared spectroscopy instrument (FT-IR) and X-ray diffractometer. Catalytic activity is examined through comparative experiments. The results show that it exhibits high catalytic activity for degradation of methylene blue (MB) in the presence of H2O2, the remaining rate of MB is 12.02% after 6 h. The reaction process conforms to the equation of pseudo-first-order kinetics, and the correlation coefficient R2> 0.99. The recycling tests for five times are also carried out and prove its reusability in catalytic application.

A comparative study on DNA/BSA binding, DNA photocleavage and antioxidant activities of water soluble peripherally and non-peripherally tetra-3-pyridin-3-ylpropoxy-substituted Mn(III), Cu(II) phthalocyanines

In this study, peripherally and non-peripherally tetra-3-pyridin-3-ylpropoxy substituted Mn(III), Cu(II) phthalocyanines and their water soluble derivatives were synthesized and characterized. To determine DNA binding mode and cleavage pathway of water soluble phthalocyanines 2a, 3a, 2b and 3b were used CT-DNA and supercoiled pBR322 plasmid DNA. The DNA binding of water soluble phthalocyanines monitored using electronic absorption titration, competitive ethidium bromide, thermal denaturation that the water soluble phthalocyanines could bind to CT-DNA via intercalation mode in order 3a > 3b > 2a > 2b. The water soluble phthalocyanines cleaved supercoiled pBR322 plasmid DNA via photocleavage mechanism induced by singlet oxygen under irradiation at 600 nm for 3a, 700 nm for 3b and 750 nm for 2a and 2b. In addition, the binding experiment of BSA showed that water soluble phthalocyanines could bind to blood plasma proteins through a static quenching mechanism. Non-peripheral tetra-substituted water soluble Cu(II) phthalocyanine 3b showed high radical scavenging activities than other water soluble phthalocyanines due to metal ion and non-peripheral position. All of these experiments claimed that non-peripheral tetra-substituted water soluble Cu(II) phthalocyanine 3b have anticancer agent potential due to efficiently biological properties.