Phthalocyanine Chloride Research Articles

Improved photovoltaic response of a near-infrared sensitive solar cell by a morphology-controlling seed layer

We demonstrate that a thin seed layer of indium phthalocyanine chloride (ClInPc) annealed under mild conditions effectively controls the morphology of both post-annealing deposited ClInPc films and ClInPc:C60 mixed films, introducing the triclinic phase into the commonly monoclinic phase dominating film. ClInPc/C60 planar solar cells and ClInPc:C60 (1:1) planar-mixed solar cells with and without the triclinic phase were studied. Increased short circuit current (Jsc), fill factor (FF), external quantum efficiency (EQE) and internal quantum efficiency (IQE) of the devices containing triclinic phase is attributed to the enhanced absorption in the near infrared (NIR) region and decreased series resistance. The correlation between open circuit voltage (Voc) and dark saturation pre-exponential factor (Jso) was analyzed to investigate Voc loss upon annealing. The overall performance of device is considerably improved by introducing the triclinic phase of ClInPc.

Vibrational spectroscopic analysis of aluminum phthalocyanine chloride. experimental and DFT study

In this work, we report a combined experimental and theoretical study of aluminum phthalocyanine chloride (AlPcCl). The FT-IR and Raman spectra of AlPcCl were recorded and analyzed. The density functional theory (DFT) computations have been performed at B3LYP/6-31g and B3LYP/6-311g to derive equilibrium geometry, vibrational wavenumbers, intensity and NLO properties.All the observed vibrational bands have been discussed and assigned to normal mode or to combinations on the basis of our DFT calculations as a primary source of attribution and also by comparison with the previous results for similar compounds.The natural bond orbital (NBO) calculations were performed to study the atomic charge distribution of the investigated compound. The calculated results showed that dipole moment of the investigated compound was 4.68 Debye and HOMO-LUMO energy gap was 2.14eV. The lowering of frontier orbital gap appears to be the cause of its enhanced charge transfer interaction.

An ex vivo study of photobiostimulation in the treatment of skin pathologies.

Photodynamic therapy (PDT) and low level laser therapy (LLLT) may mutually improve the outcomes on the healing process of chronic wounds and other skin pathologies, through processes known to stimulate the proliferation of dermal cellular structures, as well as antimicrobial application. This study proposes the use of nanoemulsion containing aluminium phthalocyanine chloride (ClAlPc) as photosensitizer (PS), to establish the most appropriate protocol for photostimulation in human skin biopsies, associated to type I collagen and elastin production. The combined effect of PS and light (diode laser at 670nm) at three different doses is compared to the effect of light itself at doses of 70, 140 and 700mJċcm-2 , 7 and 14 days after irradiation. Histological analysis reveals the increase in collagen and elastin, higher than 20%, 14 days after treatment with PS and light at 140mJċcm-2 . Higher doses of light promote an inhibitory effect, leading to tissue degradation. In addition, the expression levels of the enzymes MMP-2 and MMP-9 (Gelatinases A and B - participant in various processes including tumoral progression and wound healing) are detected by gelatin zymography, reinforcing the efficacy of the combined treatment with PS and light at the intermediate dose.

A Triple‐Collaborative Strategy for High‐Performance Tumor Therapy by Multifunctional Mesoporous Silica‐Coated Gold Nanorods

To integrate treatments of photothermal therapy, photodynamic therapy (PDT), and chemotherapy, this study reports on a multifunctional nanocomposite based on mesoporous silica‐coated gold nanorod for high‐performance oncotherapy. Gold nanorod core is used as the hyperthermal agent and mesoporous silica shell is used as the reservoir of photosensitizer (Al(III) phthalocyanine chloride tetrasulfonic acid, AlPcS4). The mesoporous silica shell is modified with β‐cyclodextrin (β‐CD) gatekeeper via redox‐cleavable Pt(IV) complex for controlled drug release. Furthermore, tumor targeting ligand (lactobionic acid, LA) and long‐circulating poly(ethylene glycol) chain are introduced via host–guest interaction. It is found that the nanocomposite can specifically target to hepatoma cells by virtue of the LA targeting moiety. Due to the abundant existence of reducing agents within tumor cells, β‐CD can be removed by reducing the Pt(IV) complex to active cisplatin drug for chemotherapy, along with the releasing of entrapped AlPcS4 for effective PDT. As confirmed by in vitro and in vivo studies, the nanocomposite exhibits an obvious near‐infrared induced thermal effect, which significantly improves the PDT and chemotherapy efficiency, resulting in a superadditive therapeutic effect. This collaborative strategy paves the way toward high‐performance nanotherapeutics with a superior antitumor efficacy and much reduced side effects.

Conductive Behavior and Morphology of Axially Modified Gallium Phthalocyanine Thin Films onto Indium Tin Oxide Substrates

Semiconductor molecular films based on a gallium phthalocyanine chloride (GaPcCl) and a bidentate amine were prepared by using vacuum thermal evaporation and electrochemical techniques in order to investigate the preferred conduction paths within the films. Scanning Electron Microscopy (SEM) and Atomic Force Microscopy (AFM) were employed to characterize the morphology of the films. The conductivity measurements were performed with two different methods in order to investigate preferential conduction directions. The film transverse conductivity was obtained by using scanning tunneling spectroscopy (STS) and the in-plane film conductivity was measured with a four-point probe system. From spectroscopy measurements, the tunneling conductance (dI/dV) was also obtained. From these results, it was found that the conductive nature of the films was strongly influenced by the deposition technique which in turn defined the morphological characteristics of the film. The evaporated method showed better conductivity response and provided semiconductor characteristics in the film transverse direction with an in-plane ohmic response. Finally, contact angle measurements were performed and showed hydrophobic characteristics in all cases.

Organic tandem Schottky junction cells with high open circuit voltage

In our previous work [Synth.Met.200(2015)99], we demonstrated dye-based tandem photovoltaic cells with vertically stacked Schottky junctions that generate open circuit voltage Uoc=1.0V. In present work, using the same concept we reached Uoc=1.92V. Such a progress is basically associated with optimization of the anode material in both subcells. Two axially substituted phthalocyanine complexes were used as absorbers: boron chloride subphthalocyanine SubPc in the bottom subcell and indium chloride phthalocyanine InClPc in the top subcell. Inorganic semiconducting oxide MoOx was introduced twice. First, MoOx layer was deposited over the ITO anode in the bottom subcell. This largely increases Uoc as compared to the archetypal Schottky-type cell ITO/SubPc/Al. For the bottom subcell with bilayer LiF/Ag cathode Uoc=1.23V. Second, MoOx was used in the composite intermediate layer (LiF/Ag/MoOx) that assembles subcells in stack, thus acting as anode buffer in the top subcell.

Mesoporous Silica Nanoparticles Loaded with Cisplatin and Phthalocyanine for Combination Chemotherapy and Photodynamic Therapy in vitro.

Mesoporous silica nanoparticles (MSNs) have been synthesized and loaded with both aluminum chloride phthalocyanine (AlClPc) and cisplatin as combinatorial therapeutics for treating cancer. The structural and photophysical properties of the MSN materials were characterized by different spectroscopic and microscopic techniques. Intracellular uptake and cytotoxicity were evaluated in human cervical cancer (HeLa) cells by confocal laser scanning microscopy (CLSM) and 3-(4,5-dimethylthiazol-2-yl)-5-(3-carboxymethoxyphenyl)-2-(4-sulfophenyl)-2H-tetrazolium (MTS) assays, respectively. The CLSM experiments showed that the MSN materials can be readily internalized in HeLa cells. The cytotoxic experiments demonstrated that, after light exposure, the combination of both AlClPc and cisplatin compounds in the same MSN platform potentiate the toxic effect against HeLa cells in comparison to the control AlClPc-MSN and cisplatin-MSN materials. These results show the potential of using MSN platforms as nanocarriers for combination photodynamic and chemotherapies to treat cancer.

Electrical, dielectric and electrochemical measurements of bulk aluminum phthalocyanine chloride (AlPcCl)

AC conductivity and the related dielectric properties of bulk aluminum phthalocyanine chloride (AlPcCl) have been studied over a temperature range (303–403 K) and frequency range (42–106 Hz). The universal power law σac(ω)=Aωs has been used to investigate dependence of AC conductivity on frequency. The variation of the frequency exponent (s) with temperature was analyzed in terms of different conduction mechanisms; the predominant conduction mechanism was found to be the correlated barrier hopping (CBH) model. The barrier height was calculated by using (CBH) model, it was found to be 1.41 eV. Dependence of σac(ω) on temperature refers to a linear increase with increasing temperature at different frequencies. The density of states N (EF) was calculated to be equal 4.11×1019 cm−3 using Elliott model. It has been found that AC activation energy decreases with increasing frequency. Dielectric values were analyzed using complex permittivity and complex electric modulus for bulk AlPcCl at different temperatures. The obtained value of HOMO–LUMO energy gap was found to be 1.48 eV.

Selective Direct N-Alkylation of Amines with Alcohols using Iron(III) Phthalocyanine Chloride under Solvent-Free Conditions

Abstract Direct N-alkylation of amines with alcohols in the presence of iron(III) phthalocyanine chloride as a catalyst in solvent-free conditions under microwave irradiation afforded the corresponding N-alkylamines in moderate to high yield with excellent selectivity.

Spectroscopic analysis of aluminum chloride phthalocyanine in binary water/ethanol systems for the design of a new drug delivery system for photodynamic therapy cancer treatment

This study evaluated the behavior of aluminum chloride phthalocyanine in a binary water/ethanol mixture using electronic absorption spectroscopy and static and time-resolved fluorescence spectroscopy. The electronic absorption spectra, resonance light scattering and fluorescence quenching of aluminum chloride phthalocyanine in water/ethanol mixtures were studied at several concentrations. The electronic absorption spectra and fluorescence quenching changed significantly at approximately 50% water (v/v). Below 50% water, the dimerization constant values were negative (−2609.2M−1 and −506.5M−1 at 30% and 40% of water, respectively), indicating that the formation of aggregates under these conditions is not favored. However, at 50% water, the dimerization constant value was estimated to be 559.7M−1, which indicates the presence of dimers. Above 60% water, the aggregation process was responsible for the balance between large complexes (such as trimers, tetramers or oligomers) formed in the medium under these conditions. The appearance of new absorption bands at 387nm and 802nm and their bathochromic shift relative to the monomer bands suggested that some J-type aggregates form. These results are relevant to understanding the behavior and use of aluminum chloride phthalocyanine in the design of new drug delivery systems for clinical application in photodynamic therapy as a new approach to treat skin cancer.

Synergistic Integration of Layer-by-Layer Assembly of Photosensitizer and Gold Nanorings for Enhanced Photodynamic Therapy in the Near Infrared.

A layer-by-layer (LbL) assembly strategy was used to incorporate high concentrations of Al(III) phthalocyanine chloride tetrasulfonic acid (AlPcS4) photosensitizer (PS) onto plasmonic Au nanorings (Au NRs) for increasing the cellular uptake of AlPcS4 and subsequently enhancing the efficacy of photodynamic therapy (PDT) of human breast cancer cells (MDA-MB-231) in the near-infrared (NIR) range. Au NRs with two layers of AlPcS4 (Au NR/(AlPcS4)2) markedly increased the cellular internalization of AlPcS4 and elevated the generation of reactive oxygen species (ROS). Quenching the photosensitivity of AlPcS4 on the Au NR surface during the uptake and then significant ROS formation only upon PS release inside the cellular compartment made it possible to achieve a high PDT specificity and efficacy. PDT of breast cancer cells following 4 h of incubation with various formula revealed the following cell destruction rate: ∼10% with free AlPcS4, ∼23% with singly layered Au NR/(AlPcS4)1 complex, and ∼50% with doubly layered Au NR/(AlPcS4)2. Incubation with Au NR/(AlPcS4)2 for an additional 2 h resulted in ∼85% cell killing, more than 8-fold increase compared to AlPcS4 alone. Together, integration of LbL of PS with Au NRs holds a significant promise for PDT therapeutic treatment of a variety of cancers.

Small-molecule organic solar cells with multiple-layer donor

Small-molecule organic solar cells (OSCs) with a multifunction three-layer donor are experimentally investigated to achieve higher power conversion efficiency. The proposed OSC has an indium tin oxide (ITO, anode)/three-layer donor/fullerene (C60, acceptor, 40 nm)/bathocuproine (BCP, cathode buffer, 10 nm)/Ag (cathode, 100 nm) structure. The three-layer donor is composed of 3-nm-thick pentacene/20-nm-thick copper phthalocyanine (CuPc)/5-nm-thick aluminum phthalocyanine chloride (ClAlPc). The OSC achieves a power conversion efficiency of 1.79%, which is 1.7 times as large as that for an OSC with a single-layer donor of 20-nm-thick CuPc. Atomic force microscopy observation is carried out to clarify in detail the surface morphology at typical organic layers. The acceptor C60 is in contact not only with ClAlPc but also with CuPc due to the vertical and wall-like growth of the ClAlPc layer. The open-circuit voltage for the OSC with the ClAlPc/C60 contact is 0.56 V, compared with 0.47 V for the OSC with the CuPc/C60 contact. The thin pentacene layer is uniformly grown on the ITO and serves to achieve a high short-circuit current density Jsc by lowering the barrier height for hole transport between ITO and CuPc. Jsc for the OSC with the thin pentacene layer is 5.60 mA/cm2, compared with 4.32 mA/cm2 for the OSC without the thin pentacene layer.

Gold(III) phthalocyanine chloride: Optical and structural characterization of thin films

In the present work, the investigation of gold(III) phthalocyanine chloride (AuClPc) which received very little attention before is progressed further using a range of optical spectroscopic techniques. Thin films of gold(III) phthalocyanine chloride were produced by organic molecular beam deposition deposition and their structure was investigated by UV–visible spectroscopy, polarization dependent Raman spectroscopy and atomic force microscopy. Experimental observations were confirmed by theoretical analysis using quantum chemical calculations; the latter were used for the detailed assignment of different bands in IR spectra of the gold(III) phthalocyanine chloride. The orientation of gold(III) phthalocyanine chloride molecules relative to the substrate surface was studied in detail using techniques based on the polarization dependent Raman spectroscopy. It was shown that gold(III) phthalocyanine chloride films deposited on quartz substrates at 100 °C exhibit a co-facial structure with the average tilt angles of Pc moieties of ∼70°.

Reactive oxygen and nitrogen species disturb Ca2+ oscillations in insulin-secreting MIN6 β-cells

Disturbances in pulsatile insulin secretion and Ca2+ oscillations in pancreatic β-cells are early markers of diabetes, but the underlying mechanisms are still incompletely understood. Reactive oxygen/nitrogen species (ROS/RNS) are implicated in reduced β-cell function, and ROS/RNS target several Ca2+ pumps and channels. Thus, we hypothesized that ROS/RNS could disturb Ca2+ oscillations and downstream insulin pulsatility. We show that ROS/RNS production by photoactivation of aluminum phthalocyanine chloride (AlClPc) abolish or accelerate Ca2+ oscillations in the MIN6 β-cell line, depending on the amount of ROS/RNS. Application of the sarcoplasmic/endoplasmic reticulum Ca2+ ATPase (SERCA) inhibitor thapsigargin modifies the Ca2+ response to high concentrations of ROS/RNS. Further, thapsigargin produces effects that resemble those elicited by moderate ROS/RNS production. These results indicate that ROS/RNS interfere with endoplasmic reticulum Ca2+ handling. This idea is supported by theoretical studies using a mathematical model of Ca2+ handling adapted to MIN6 cells. Our results suggest a putative link between ROS/RNS and disturbed pulsatile insulin secretion.

Electrical and photovoltaic characteristics of indium phthalocyanine chloride/p-Si solar cell

Hybrid (organic/inorganic) heterojunction solar cell based on indium phthalocyanine chloride derivative (InPcCl-D) deposited by thermal evaporation technique onto p-type silicon single crystal wafer has been fabricated. The cell was characterized by current–voltage and capacitance–voltage measurements. The dark current–voltage characteristics of Au/InPcCl-D/p-Si/Al heterojunction device were measured at different temperatures. The device showed rectification behavior with a rectification ratio of 102 at ±1V determined at room temperature. The dominant conduction mechanisms operating consequently are the thermionic emission and the single-trap space-charge limited current. The junction parameters such as diode ideality factor, potential barrier height and series resistance are estimated as a function of temperature. The device is non ideal in showing ideality factor of 3.28 at room temperature. The temperature dependence of the ideality factor, barrier height and series resistance indicates the formation of non homogenous barrier height in the junction. The space charge limited current conduction mechanism showed that the trap concentration is 1.53×1025m−3 and it lies at 0.11eV above the valence band edge. Capacitance–voltage measurements showed the abrupt nature of the junction and the built-in potential is determined. The value of the built in potential and carrier concentration are estimated as 0.85V and 3.31×1022m−3, respectively. Under illumination intensity of 100W/m2, the device showed photovoltaic behavior with open circuit voltage, Voc, and short circuit current density, Jsc, of 0.352V and 7.6mA/cm2, respectively. The values of filling factor, FF, and photo-electrical conversion efficiency, η, are estimated as 0.31 and 2.96%, respectively.

Structural and optical properties of nanocrystalline aluminum phthalocyanine chloride thin films

Thin films of aluminum phthalocyanine chloride (AlPcCl) were fabricated, with different thicknesses (109–518nm) using thermal evaporation technique. Structural and optical properties of AlPcCl thin films were investigated. The material in powder form showed a polycrystalline nature with monoclinic structure. Miller indices, hkl, values for each diffraction line in X-ray diffraction (XRD) spectrum were calculated. The field emission scanning electron microscope (FESEM) showed the nanostructure property of the as-deposited thin films. The optical properties of the thin films were studied by the spectrophotometric measurements of the transmittance, T, and the reflectance, R, at the normal incidence of the light in the spectral range 200–2500nm. The refractive and absorption indices of the thin films were calculated and were found to be independent of film thickness of 109–518nm. The films exhibited indirect allowed inter-band transitions. The optical band gaps transitions were calculated as 1.42, 2.87 and 3.69eV, respectively. Also, different dispersion and absorption parameters were determined for thin films of AlPcCl.

Enhancement of the photokilling effect of aluminum phthalocyanine in photodynamic therapy by conjugating with nitrogen-doped TiO2 nanoparticles

As a second-generation photodynamic therapy (PDT) photosensitizer, aluminum phthalocyanine chloride tetrasulfonate (Pc) has gained great attention due to its high absorption at the red light region. Yet, its application in PDT is strongly limited by its low cellular uptake efficiency. In this report, nitrogen-doped TiO2 nanoparticles (N–TiO2) conjugated with Pc are synthesized by a two-step surface modification method. The N–TiO2–Pc products are characterized by Zeta potential, transmission electron microscopy and UV–vis absorption spectroscopy. The cellular uptake, intracellular distribution, cytotoxicity and the photokilling effect of the nanoparticles are studied on different cancer cell lines. Compared with Pc, the absorption spectrum of N–TiO2–Pc expands from red to UV region, resulting in a higher production of reactive oxygen species under visible light irradiation. In addition, the cellular uptake of Pc is largely improved by its carrier N–TiO2. The photokilling efficiency of N–TiO2–Pc is over ten times higher than that of Pc. The results suggest that N–TiO2–Pc is an excellent candidate as a photosensitizer in PDT.

Gamma radiation-induced changes on the structural and optical properties of aluminum phthalocyanine chloride thin films

Thin films of aluminum phthalocyanine chloride (AlPcCl) were prepared by thermal evaporation technique under high vacuum at room temperature. The prepared films were divided into two groups for study; the first was the as – deposited films, the second group was irradiated in gamma cell type 60Co source in air at room temperature with different absorbed doses (20–60kGy). The surface morphology of γ-irradiated film was observed with a higher aggregation compared with as-deposited film with an average particles size of (10–28nm). The optical parameters were obtained using spectrophotometric measurements of the transmittance and reflectance at normal incidence of light in wavelengths range of 200–2500nm. The type of optical transition was found to be an indirect allowed transition, the band gaps decrease with increasing γ-irradiation doses. The calculated dispersion parameters of AlPcCl films decreased with increasing the γ-irradiation dose. The disagreement between the obtained values of ε∞ and εL may be attributed to the lattice vibration and free carrier contribution.

Formulation of Aluminum Chloride Phthalocyanine in Pluronic(™) P-123 andF-127 Block Copolymer Micelles: Photophysical properties and Photodynamic Inactivation of Microorganisms.

Aluminum Chloride Phthalocyanine (AlPcCl) can be used as a photosensitizer (PS) for Photodynamic Inactivation of Microorganisms (PDI). The AlPcCl showed favorable characteristics for PDI due to high quantum yield of singlet oxygen (ΦΔ ) and photostability. Physicochemical properties and photodynamic inactivation of AlPcCl incorporated in polymeric micelles of tri-block copolymer (P-123 and F-127) against microorganisms Staphylococcus aureus, Escherichia coli and Candida albicans were investigated in this work. Previously, it was observed that the AlPcCl undergoes self-aggregation in F-127, while in P-123 the PS is in a monomeric form suitable for PDI. Due to the self-aggregation of AlPcCl in F-127, this formulation did not show any effect on these microorganisms. On the other hand, AlPcCl formulated in P-123 was effective against S.aureus and C.albicans and the death of microorganisms was dependent on the PS concentration and illumination time. Additionally, it was found that the values of PS concentration and illumination time to eradicate 90% of the initial population of microorganisms (IC90 and D90 , respectively) were small for the AlPcCl in P-123, showing the effectiveness of this formulation for PDI.

Phthalocyanine photosensitizers as contrast agents for in vivo photoacoustic tumor imaging.

There is a need for contrast agents for non-invasive diagnostic imaging of tumors. Herein, Multispectral Optoacoustic Tomography (MSOT) was employed to evaluate phthalocyanines commonly used in photodynamic therapy as photoacoustic contrast agents. We studied the photoacoustic activity of three water-soluble phthalocyanine photosensitizers: phthalocyanine tetrasulfonic acid (PcS4), Zn(II) phthalocyanine tetrasulfonic acid (ZnPcS4) and Al(III) phthalocyanine chloride tetrasulfonic acid (AlPcS4) in phantom and in tumor-bearing mice to investigate the biodistribution and fate of the phthalocyanines in the biological tissues. PcS4 was observed to grant good contrast between the different reticuloendothelial organs and accumulate in the tumor within an hour of post-administration. ZnPcS4 and AlPcS4 offered little contrast in photoacoustic signals between the organs. PcS4 is a promising photoacoustic contrast agent and can be exploited as a photodiagnostic agent.