Soluble Phthalocyanine Derivatives Research Articles

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.

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.

Ambipolar Carrier Mobility in Binary Blend Thin Film of Non-Peripheral Alkylphthalocyanines

Charge carrier mobility in blend films of two types of soluble phthalocyanine derivatives with different substituent length, 1, 4, 8, 11, 15, 18, 22, 25-octapentyl-phthalocyanine (C5PcH2) and 1, 4, 8, 11, 15, 18, 22, 25-octahexyl-phthalocyanine (C6PcH2) has been investigated. The charge carrier mobility was measured by the time-of-flight technique. In the case of C5PcH2 blend ratio below 25 mol%, the high mobility, such as 0.8-1.1 cm2V-1s-1 for hole and 0.6 cm2V-1s-1 for electron, were obtained at room temperature. In the thin films with C5PcH2 above 30 mol%, the charge carrier mobility decreased by one order of magnitude and had the different temperature dependence from that below 25 mol%. The marked change of the charge carrier mobility depending on the blend ratio of phthalocyanine derivatives has been discussed by taking the miscibility and the molecular packing structure into consideration.

Thermal annealing effects on non-peripheral octahexylphthalocyanine doped polymer bulk heterojunction solar cells

We investigated the thermal annealing temperature dependence of the photovoltaic properties of organic thin film solar cells based on a bulk heterojunction of poly(3-hexylthiophene) (P3HT) and 1-(3-methoxy-carbonyl)-propyl-1-1-phenyl-(6,6)C61 (PCBM) doped with the soluble phthalocyanine derivative 1,4,8,11,15,18,22,25-octahexylphthalocyanine (C6PcH2). The photocurrent density was increased by 45% and the power conversion efficiency was improved to 3.9% by annealing at 130 °C. The annealing temperature dependence of the photovoltaic properties is discussed by considering the result of X-ray diffraction and photoluminescence measurements.

Miscibility in binary blends of non-peripheral alkylphthalocyanines and their application for bulk-heterojunction solar cells

The fabrication of small-molecule bulk-heterojunction solar cells utilizing a mixed donor material composed of two types of soluble phthalocyanine derivatives with different substituent length has been studied. The power conversion efficiency (PCE) and short-circuit current density (Jsc) of the solar cells fabricated using the mixed donor material with an optimized mixture ratio reached 3.8% and 9.2mA/cm2, respectively, which were superior to those of organic solar cells utilizing each type of phthalocyanine derivative as a single donor material. The improvement of PCE and Jsc has been discussed from the viewpoints of the miscibility and carrier transport properties of the mixed donor material.

Solvent Effects on Solution-Processable Bulk Heterojunction Organic Solar Cells Utilizing 1,4,8,11,15,18,22,25-Octahexylphthalocyanine

Bulk heterojunction organic solar cells utilizing soluble phthalocyanine derivative, 1,4,8,11,15,18,22,25-octahexylphthalocyanine (C6PcH2), have been fabricated by solution process with various solvents, and their photovoltaic properties have been studied. It is found that the marked differences on the morphologies of the bulk heterojunction film, such as the surface roughness, crystallinity and crystallite size, exist and relate with the boiling points of the solvents. The solvent effects on the photovoltaic properties have been discussed by taking the exciton dissociation efficiency and carrier transport efficiency into consideration.

Dependence of alkyl-substituent length for bulk heterojunction solar cells utilizing 1,4,8,11,15,18,22,25-octaalkylphthalocyanine

Bulk heterojunction organic thin-film solar cells utilizing soluble phthalocyanine derivatives, 1,4,8,11,15,18,22,25-octaalkylphthalocyanine (CnPcH2, n = 6, 7, 9, 10), were investigated. Two broad peaks existing in the external quantum efficiency spectra almost correspond to the Q-band and B-band of CnPcH2. The solar cell utilizing C6PcH2 had the best photovoltaic properties as evidenced by open-circuit voltage, short-circuit current density, fill factor, and energy conversion efficiency. Almost the same photovoltaic properties were observed in the solar cells utilizing C9PcH2 and C10PcH2. We discuss the photovoltaic properties by taking into consideration the crystal structure and electronic state of CnPcH2 from the results of the absorbance spectra, X-ray diffraction measurement, and polarization microscope observation.

Acceptor Material Dependence of Photovoltaic Properties in Bulk Heterojunction Organic Thin Film Solar Cells Utilizing Soluble Octahexylphthalocyanine

Dependence of photovoltaic properties in bulk heterojunction organic thin film solar cells utilizing soluble phthalocyanine derivative, 1,4,8,11,15,18,22,25-octahexylphthalocyanine (C6PcH2) on acceptor materials have been investigated. As acceptor materials, we have adopted four fullerene derivatives, such as, 1-(3-methoxy-carbonyl)-propyl-1-1-phenyl-(6,6)C61 (PCBM), 1-[3-(methoxycarbonyl)propyl]-1-phenyl)-[6.6]C62 (bis[60]PCBM), Indene-C60 Bisadduct (ICBA), and 1-(3-methoxycabonyl)-propyl-1-1-phenyl-(6,6)C71 ([70]PCBM), which possess different LUMO or HOMO levels in their electric energy structures. The open circuit voltage (Voc) of the solar cells was strongly dependent on the acceptor materials, and high Voc of 0.97V could be achieved by using bis[60]PCBM. The photovoltaic properties, such as, Voc, of the solar cells with the bulk heterojunction of C6PcH2 and fullerene derivatives have been discussed by taking the energy diagrams of the materials used in this study into consideration.

Non-peripheral octahexylphthalocyanine doping effects in bulk heterojunction polymer solar cells

The improvement of long-wavelength sensitivity in bulk heterojunction organic thin-film solar cells based on poly(3-hexylthiophene) (P3HT) by the addition of the soluble phthalocyanine derivative, 1,4,8,11,15,18,22,25-octahexylphthalocyanine (C6PcH 2) is reported. C6PcH 2 possesses near-infrared absorption and can be mixed with a P3HT:1-(3-methoxy-carbonyl)-propyl-1-1-phenyl-(6,6)C61 (PCBM) bulk heterojunction active layer. By doping C6PcH 2, the photosensitivity in the long-wavelength region was improved, and the energy conversion efficiency reached 3.0% at a composition ratio of P3HT:C6PcH 2:PCBM = 10:3:10. We discuss the principle of photoconversion in the bulk heterojunction solar cell based on the P3HT:C6PcH 2:PCBM active layer by taking into consideration the existence of both highly ordered P3HT domains and hexagonal columnar structures of C6PcH 2, and the microphase separation of P3HT and C6PcH 2 in the active layer.

Bulk heterojunction organic solar cells utilizing 1,4,8,11,15,18,22,25-octahexylphthalocyanine

Bulk heterojunction solar cells utilizing soluble phthalocyanine derivative, 1,4,8,11,15,18,22,25-octahexylphthalocyanine (C6PcH 2) have been investigated. The active layer was fabricated by spin-coating the mixed solution of C6PcH 2 and 1-(3-methoxy-carbonyl)-propyl-1-1-phenyl-(6,6)C61 (PCBM). The photovoltaic properties of the solar cell with bulk heterojunction of C6PcH 2 and PCBM demonstrated the strong dependence of active layer thickness, and the optimized active layer thickness was clarified to be 120 nm. By inserting MoO 3 hole transport buffer layer between the positive electrode and active layer, the FF and energy conversion efficiency were improved to be 0.50 and 3.2%, respectively. The tandem organic thin-film solar cell has also been studied by utilizing active layer materials of C6PcH 2 and poly(3-hexylthiophene) and the interlayer of LiF/Al/MoO 3 structure, and a high V oc of 1.27 V has been achieved.

5-Hexylthiophene-fused porphyrazines: new soluble phthalocyanines for solution-processed organic electronic devices

5-Hexylthiophene-fused porphyrazines were designed and synthesized as novel soluble phthalocyanine derivatives. Single-crystal X-ray structural analyses indicated that they have a well-ordered structure in the solid state in spite of the existence of disorder in the thiophene-fused porphyrazine core. Due to the high solubility and improved molecular ordering, the present 5-hexylthiophene-fused porphyrazines showed comparable performance to vapor-processable phthalocyanines as solution-processable organic semiconductors: solution-processed OFETs showed mobility of up to 0.2 cm2V−1 s−1.

PV and magnetic field effects in poly(3-hexylthiophene)-fullerene cells doped with phthalocyanine soluble derivative

An attempt was made to widen the photosensitivity spectral range of poly(3-hexylthiophene)-fullerene blend by adding an extra electron donor — a newly synthesized soluble phthalocyanine derivative (SnClPc) having the electron absorption band at 708 nm. As the electron acceptor, home-synthesised di(ethoxycarbonyl) methano-fullerene carboxylate (C 61 (CO 2 Et) 2 ) was used, and as the hole transporter — the regioregular poly 3-hexylthiophene (P3HT). The sandwich-type samples were prepared on an ITO glass substrate by coating it with a 30–50 nm thick PEDOT:PSS layer followed by a ~100 nm thick P3HT:C 61 (CO 2 Et) 2 :SnClPc blend. For the top electrodes In or Au were used. Spectral dependences of the PV effect and of the influence of external magnetic field (0–3000 Oe) on it were studied in the 370–1000 nm spectral range in vacuum of ~10 -6 Torr. Significant photosensitivity of the blend was observed in the 370–800 nm spectral range. However, the short-circuit photocurrent quantum efficiency evaluated for absorbed light was found to be 4 times higher for illumination in the P3HT absorption band as compared with that in the SnClPc band. The observed magnetic field effect shows that the low IPCE values may be explained by the space charge formation in the samples, leading to a strong geminate recombination of CP states.

Field-Effect Transistors Based on Langmuir−Blodgett Films of Phthalocyanine Derivatives as Semiconductor Layers

Two soluble phthalocyanine derivatives, 2,9,16-tri(tert-butyl)-23-(10-hydroxydecyloxy) phthalocyanine (1) and 2,9,16-tri(tert-butyl)-23-(10-hydroxydecyloxy) copper phthalocyanine (2) were used as semiconductor layers in organic thin-film transistors (OTFTs) based on their Langmuir−Blodgett (LB) films. From the π−A curves, we can conclude that the phthalocyanine 1 and 2 molecules are in a titled arrangement at the air−water interface. The molecular ordering in the LB multilayer films on the SiO2 substrate was examined by using UV−Vis absorption spectra and atomic force microscopy (AFM). The highest occupied molecular orbital and the lowest unoccupied molecular orbital were determined, and the energy band diagram of their OTFTs can be deduced by the cyclic voltammetric measurements. The LB films of phthalocyanine 1 and 2 were subsequently made into p-channel field-effect transistors, which were generally operated in the enhanced mode. The channel mobilities of phthalocyanine 1 and 2 were calculated to be about 4.8 × 10-5 cm2 V-1 s-1 and 4.0 × 10-4 cm2 V-1 s-1, respectively.

Syntheses and characterization of soluble phthalocyanine derivatives for organic electroluminescent devices

Metal–4,4′,4″,4‴-tetraamino phthalocyanines (MT4APc) for organic electroluminescent devices were prepared and characterized, where M is Co, Cu and Zn. The phthalocyanines were soluble in common organic solvents, and thus easily coated with 2,2′-bis(3,4-dicarboxy-phenyl) hexafluoroisopropanedianhydride–2,4,6-trimethyl-1,3-phenylene-diamine (6FDA–3MPDA) polyimide, a polymer matrix, onto an ITO glass by the spin-coating method. The structures of the devices used in this work were ITO/Alq3/Al and ITO/TPD and MT4APc-dispersed 6FDA–3MPDA PI/Alq3/Al. The phthalocyanines-dispersed polyimide double-layer devices showed lower turn-on voltages and higher relative efficiencies than the single-layer device without phthalocyanines. The relative efficiency of MT4APc and TPD as a hole-transporting layer was found to be in the order CuT4APc>CoT4APc≈TPD>ZnT4APc.