Thin films of peripheral and non-peripheral tetra-substituted copper phthalocyanines [CuPcR4, R =-O(CH2CH2O)(3)CH3 or -S(CH2CH2O)(3)CH3] and their hybrids with single walled carbon nanotubes( SWCNT) have been investigated as optical active layers for amines vapours detection. Adsorption of amines onto the films' surfaces has been realized by monitoring changes in the phase shift (Delta(lambda)) of total internal reflection ellipsometry spectra. Methylamine has shown higher sensitivity and lower response time among the studied three amines. The steric hindrance provided by the shapes of the secondary and tertiary amine molecules is thought to decrease the interaction with films' surfaces as compared to methylamine. For all active layers used in this study, the sensitivity of SWCNT/CuPcR4 hybrid films was higher than the sensitivity of pristine CuPcR4 films with clear recovery in the Delta(lambda) spectra after flushing the cell with air. The lower response time at 40 ppm is found to be 66 s and the highest sensitivity is 0.000325/ppm towards methylamine vapour. (C) 2014 Elsevier B.V. All rights reserved.

Tetra-substituted copper phthalocyanine (CuPcR4, R = −S(CH2)15CH3) has been prepared and characterised by UV–Vis, FT-IR and mass-spectrometry. Hybrid materials were produced by mixing CuPcR4 with acidified single-walled carbon nanotubes (SWCNTs) and characterised by UV–Vis absorption spectroscopy, scanning electron microscopy and atomic force microscopy. Thin films of pristine CuPcR4 and SWCNT/CuPcR4 were prepared by spin coating onto gold-coated glass slides and applied as active layers to detect pentachlorophenol (PCP) in water utilizing total internal reflection ellipsometry (TIRE) technique. Different concentrations of PCP in water ranging from 0.5 to 10 μg/l have been examined in the current work. It is revealed that the phase shift (Δ(λ)) spectra of SWCNT/CuPcR4 films were two times larger than the shifts produced by the pristine CuPcR4 films with clear recovery in the Δ(λ) spectra after flushing the cell with water. The adsorption of PCP on both types of films is discussed and films' sensitivity was determined using the change in films' refractive index.

The hybrids of single walled carbon nanotubes (SWCNTs) with symmetrically octasubstituted zinc phthalocyanine (2) bearing eight polyoxyethylene groups and asymmetrically substituted zinc phthalocyanine (1) bearing one pyrene and six polyoxyethylene groups as side chains have been prepared and characterized by Raman and fluorescence emission spectroscopies, scanning electron and transmission electron (SEM and TEM) microscopies, and thermogravimetric analysis. The pyrene group was chosen to enhance the interaction of phthalocyanine molecules with SWCNTs. Thin films of pristine SWCNTs and SWCNT/ZnPc hybrids were prepared by drop casting onto interdigitated electrodes and employed as active layers to detect ammonia vapour (1-200 ppm) by measuring electrical resistance changes. A comparative analysis of sensors' response of pristine SWCNTs and SWCNT/ZnPc hybrid films to ammonia vapour was carried out to demonstrate the synergic effect between SWCNTs and ZnPc derivatives. Influence of pyrene substituent in the phthalocyanine ring on the hybrid formation and their sensor response has also been discussed. (C) 2014 Elsevier B.V. All rights reserved.

Photodynamic therapy (PDT) and vascular-disrupting agents (VDA) each have their advantages in the treatment of solid tumors, but also present drawbacks. In PDT, hypoxia at the center of the tumor limits conversion of molecular oxygen into singlet oxygen, while VDAs are deficient at affecting the rim of the tumor. A phthalocyanine-chalcone conjugate combining the VDA properties of chalcones with the PDT properties of phthalocyanines was designed to address these deficiencies. Its vascular targeting, photophysical, photochemical, photodynamic activities are reported herein.

A novel thiol functionalized zinc phthalocyanine complex (ZnPcSH) is reported in this work. This complex was conjugated to gold nanoparticles. The photophysical and photochemical properties of the complex and the conjugate were investigated. Upon conjugation a blue shift was observed from the UV-Vis spectra. The conjugate showed a decrease in the fluorescence quantum yield and lifetime. An increase in the triplet quantum yield and lifetime was observed for ZnPcSH following conjugation to gold nanoparticles. Both ZnPcSH and its conjugate with gold nanoparticles showed high singlet oxygen quantum yields with the conjugate being higher than the Pc alone.

A novel pyrene containing asymmetric Zn(II) phthalocyanine (AB3 type) was synthesized and characterized by various spectroscopic techniques as well as elemental analysis. A symmetric polyoxyethylene substituted Zn(II) phthalocyanine (B4 type) derivative was also prepared in order to compare the properties and determine the effect of the pyrene group on the phthalocyanine molecule. Composites of synthesized zinc(II) phthalocyanine-single wall carbon nanotubes (ZnPc-SWCNTs) containing 1 and 2 wt% carbon nanotubes were prepared by mixing these two components in dichloromethane followed by removal of the solvent and drying under vacuum. The liquid crystalline properties of the pure compounds and their composites were investigated in comparison with symmetric polyoxyethylene substituted Zn(II) phthalocyanine (B4 type) by using polarized optical microscopy, differential scanning calorimetry and X-ray diffraction analysis. The distribution of the SWCNTs in the ordered matrix of the columnar mesophase of these derivatives was studied by the method of polarized Raman spectroscopy and scanning electron microscopy (SEM). It was shown that the nature of the mesophases was not altered in these composites. The I(V) dependencies for the films deposited onto interdigitated electrodes were measured and it was shown that the lateral conductivity tends to increase with increasing SWCNT concentration.

Octasubstituted copper(II) phthalocyanines containing alkylthio-, alkyloxy-, (trioxyethylene)thio- and (trioxyethylene)oxy- substituents in peripheral positions have been synthesized and characterized using UV-vis, IR, and mass spectroscopies. The mesogenic properties of the copper(II) phthalocyanines have been studied by differential scanning calorimetry, polarizing optical microscopy, and X-ray diffraction. The effect of the nature of substituents in the phthalocyanine ring on the liquid crystalline properties and the orientation of the molecules in thin films have also been investigated using a range of spectral methods as well as by X-ray diffraction analysis. Visible absorption spectroscopy yielded an evidence of a thermally induced molecular reorganization in the films. Polarized Raman spectroscopy was used to study the preferential orientation of molecules relative to the substrate surface. Influence of the nature of substituents in the phthalocyanine molecule in the thin films conductivity was also investigated. (C) 2012 Elsevier B.V. All rights reserved.

Octasubstituted lead(II) phthalocyanines containing alkylthio- and alkoxy-groups in peripheral positions have been synthesized and characterized using H-1 and C-13 NMR, UV-Vis, IR and mass spectroscopies as well as elemental analysis. The mesogenic properties of the octasubstituted lead(II) phthalocyanines have been investigated by differential scanning calorimetry, polarizing optical microscopy, and X-ray diffraction. The sandwich structures ITO/PbPc/In were prepared to investigate the J(V) characteristics of thin films of these molecules. The dissimilar behavior of the films before and after heat-treatment is expected to result in changing the alignment inside the columnar stacking of the molecules in the films.

A phthalocyanine-chalcone conjugate has been designed to combine the vascular disrupting effect of chalcones with the photodynamic effect of phthalocyanines. This potential dual photodynamic and antiangiogenic agent was obtained by the condensation of a tetrahydroxylated non-peripherally substituted Zn(ii) phthalocyanine with an amino chalcone converted into the corresponding activated isocyanate. The conjugate was fully characterized.

In this study, liquid crystalline copper phthalocyanine and single walled carbon nanotubes were dispersed in solution to prepare novel composites. Thin films of these composites prepared by solving of the composite in dimetylformamide and then by spin coating the solution onto the substrates were studied by the methods of polarizing microscopy, polarized Raman and optical absorption spectroscopies. It was shown that pure CuPcR4forms the films with a herringbone arrangement of phthalocyanine molecules within adjacent columns. An addition of carbon nanotubes (0.5-2 wt %) to CuPcR4leads to formation of the films with edge-on orientation of the molecules. The higher conductivity values were found for the films of phthalocyanine containing SWCNT. The lateral conductivity tends to decrease with the increase of SWCNT concentration from 0.5 to 2 wt %.

Peripherally and nonperipherally tetrakisoctylthio- and tetrakisoctyloxy-substituted lead(II) phthalocyanines (PbPcs) were synthesized and characterized using elemental analysis, nuclear magnetic resonance, ultra violet-visible (UV-Vis), infrared (IR), and mass spectroscopies. The mesogenic properties of PbPcs were studied by differential scanning calorimetry, polarized optical microscopy, and x-ray diffraction. The effects of the substitution position and nature of linkage heteroatom on the liquid-crystalline properties and the orientation of the molecules were also studied. Visible absorption spectroscopy yielded an evidence of a thermally induced molecular reorganization in the films. Reflection-absorption IR spectroscopy was used to study the preferential orientation of molecules relative to the substrate surface. The intense bands in the IR spectra of the PbPcs were assigned with the aid of quantum chemical (density functional theory) computations.

Three Zn(II) phthalocyanines substituted by hydroxyl-terminated tetraethylene glycol chains have been synthesized. In order to evaluate the potential of these highly water-soluble phthalocyanines as type II-photosensitisers for photodynamic therapy, their structure-activity relationship was assessed by determining relevant photophysical and photochemical properties, such as their aggregation behaviour in aqueous buffers, their fluorescence properties and their efficiency with regard to the generation of singlet oxygen. In addition, evidence for a negligible interaction with plasma proteins in undiluted human plasma was obtained using a recently developed bioanalytical method and compared with the fluorescence quenching approach. These results combined with in vitro data regarding the phototoxicity of these phthalocyanines against HT-29 cancer cells provide evidence for the relevance of the non-peripherally substituted derivative for further in vivo investigations.

Novel 2,3,9,10,16,17,23,24-octaamino substituted Ni(II) phthalocyanine (2) was synthesized from tosylamido (tosyl: toluene-p-sulphonyl) derivative by the cleavage of tosyl groups in the presence of 90% sulfuric acid. Octa-hexanoylamido Ni(II) phthalocyanine (3a) and octa-lauroylamido Ni(II) phthalocyanine (3b) were obtained by reacting of octa-amino Ni(II) phthalocyanine (2) with hexanoyl chloride and lauroyl chloride, respectively. The new compounds have been characterized by elemental analysis, FT-IR, NMR and UV-vis spectroscopy and mass spectrometry. The aggregation behaviors of new compounds were investigated by UV-vis spectroscopy.

The title complex, [Cu2(C22H16N4O4S2)2(NH3)4]·2H2O, is a centrosymmetric dimer. The two copper ions are bridged by two 4,5-dicyano-N,N′-bis­(p-tolyl­sulfonyl)-o-phenyl­ene­di­am­ine ligands; the Cu⋯Cu distance is 8.749 (1) A. Each copper ion is in a distorted square-pyramidal geometry, defined by two N atoms from one ligand, two N atoms from two coordinated ammonia mol­ecules and one CN from the other ligand apically. The hydrogen-bonding network leads to a layered structure.