Devrim Atilla

Synthesis, photophysical and photochemical properties of poly(oxyethylene)-substituted zinc phthalocyanines

The synthesis, photophysical and photochemical properties of the tetra- and octa-poly(oxyethylene)substituted zinc (II) phthalocyanines are reported for the first time. The new compounds have been characterized by elemental analysis, IR, 1H and 13C NMR spectroscopy, electronic spectroscopy and mass spectra. General trends are described for photodegradation, singlet oxygen, triplet state and fluorescence quantum yields, and triplet and fluorescence lifetimes of these compounds in dimethylsulfoxide (DMSO). Photophysical and photochemical properties of phthalocyanine complexes are very useful for PDT applications. The effects of the substituents on the photophysical and photochemical parameters of the zinc(II) phthalocyanines (3a, 5a and 6a) are also reported. The singlet oxygen quantum yields (Phi(Delta)), which give an indication of the potential of the complexes as photosensitizers in applications where singlet oxygen is required (Type II mechanism) ranged from 0.60 to 0.72. Thus, these complexes show potential as Type II photosensitizers. The fluorescence of the complexes was quenched by benzoquinone (BQ).

Recent studies chemical sensors based on phthalocyanines

Phthalocyanines (Pcs) are organic compounds able to act as chemical recognition systems because of the various physical effects induced in them by interaction with a large number of gases. The gas response, stability and other sensing characteristics of the Pc films are affected by many factors, such as film morphology, molecular orientation and so on. The interaction between the Pc coatings and the gas molecules may be classified in terms of irreversible chemical affinity, reversible (usually charge transfer) chemical reaction or sorption. The nature of the interactions between the coating and vapor molecules determines the selectivity, sensitivity, signal kinetics, and the reversibility of the sensor. The magnitude of these interactions may be conveniently described in the frame of the linear sorption energy relationship (LSER) model that has been shown to be very efficient at predicting the behavior of polymer-based sensors. In this paper, the effect of coating parameters on sensing properties and sensing mechanism are reviewed. We have proposed an alternative way to achieve optimal sensor performance: liquid crystalline Pcs forming self-ordered thin films of defined area and thickness simply by heating the sample over the phase transition temperature and synthetized mesomorphic and functionalized phthalocyanines, to develop sensors based on mass-sensitive transducers (quartz crystal microbalance, QCM). Phthalocyanines used are discussed in terms of their physical and chemical properties, as well as their sensing properties: sensitivity, selectivity and reversibility. We showed our results with LSER and the results are in good agreement with this theory.

Tetra-triethyleneoxysulfonyl substituted zinc phthalocyanine for photodynamic cancer therapy

Photodynamic therapy (PDT) has emerged as an effective and minimally invasive treatment option for several diseases, including some forms of cancer. However, several drawbacks of the approved photosensitizers (PS), such as insufficient light absorption at therapeutically relevant wavelengths hampered the clinical effectiveness of PDT. Phthalocyanines (Pc) are interesting PS-candidates with a strong light absorption in the favourable red spectral region and a high quantum yield of cancer cell destroying singlet oxygen generation. Here, we evaluated the suitability of tetra-triethyleneoxysulfonyl substituted zinc phthalocyanine (ZnPc) as novel PS for PDT. ZnPc-induced phototoxicity, induction of apoptosis as well as cell cycle arresting effects was studied in the human gastrointestinal cancer cell lines of different origin. Photoactivation of ZnPc-pretreated (1-10 μM) cancer cells was achieved by illumination with a broad band white light source (400-700 nm) at a power density of 10 J/cm(2). Photoactivation of ZnPc-loaded cells revealed strong phototoxic effects, leading to a dose-dependent decrease of cancer cell proliferation of up to almost 100%, the induction of apoptosis and a G1-phase arrest of the cell cycle, which was associated with decrease in cyclin D1 expression. By contrast, ZnPc-treatment without illumination did not induce any cytotoxicity, apoptosis, cell cycle arrest or decreased cell growth. Antiangiogenic effects of ZnPc-PDT were investigated in vivo by performing CAM assays, which revealed a marked degradation of blood vessels and the capillary plexus of the chorioallantoic membrane of fertilized chicken eggs. Based on our data we think that ZnPc may be a promising novel photosensitizer for innovative PDT.

A comparative study on photophysical and photochemical properties of zinc phthalocyanines with different molecular symmetries

The five possible non-peripherally substituted zinc(II) phthalocyanines with different molecular symmetries (Pc1–Pc5) were synthesized from statistical condensation of the phthalonitrile derivatives (A and B). 2-[2-(2-ethoxyethoxy)ethoxy]-1-[2-((2-ethoxyethoxy)-ethoxy)ethoxymethyl]ethyloxy and 2′-[(tert-butoxycarbonyl)amino]ethoxy groups were used as substituents. The structures of the new compounds were characterized using elemental analysis and spectroscopic data including IR, 1H and 13C NMR, electronic absorption and mass spectra. The photophysical and photochemical properties of these new compounds were investigated in DMSO. The effect of the molecular symmetry of phthalocyanine molecules on the photophysical and photochemical properties was compared in this study.

Synthesis, characterization and aggregation behavior of Ni(II) and Zn(II) phthalocyanines with peripheral monoazacrown ethers

The synthesis of metallo derivatives (Ni, Zn) of phthalocyanines (pcs) obtained from 4,5-dicyanobenzomonoazacrown ether substituted with long alkyl chains (5a-d) are described. The new compounds have been characterized by elemental analysis, 1H, 13C NMR, MS, IR and UV-vis spectroscopy techniques. The aggregation properties and alkali metal interaction of the pcs (6a-d and 7a-d) were investigated.

Volatile organic compounds sensing properties of tetrakis(alkylthio)-substituted lutetium(III) bisphthalocyanines thin films.

The effect of volatile organic compounds (VOCs) such as acetone, methanol, ethanol, chloroform, carbon tetrachloride, dichloromethane, and hexane on electrical conductivity of thin films of bis[tetrakis(alkylthio)phthalocyaninato]lutetium(III) double decker complexes [(C(n)H(2n+1)S)(4)Pc](2)Lu(III) was investigated. The [(C(n)H(2n+1)S)(4)Pc](2)Lu(III) molecules substituted with different alkylthia chains (n=6, 8, 10, 12, and 16) were coated on interdigital transducers using a jet spray technique. A change (increase or decrease) in the conductivity of the [(C(n)H(2n+1)S)(4)Pc](2)Lu(III) films was observed depending on the concentration of the VOCs, which was ranging from 500 to 5000 ppm. The decrease in the conductivity of the sensors for the dissolvent of the compounds (chloroform, carbon tetrachloride, dichloromethane and hexane) could be related to swelling of the films. On the other hand, the increase in the conductivity of the sensors for the other VOCs (acetone, methanol and ethanol) could be resulted from that the VOCs act as electron donors and/or acceptors in the films. A linear relationship between the sensor response and concentration of the VOC vapors is obtained. The sensitivities of the [(C(n)H(2n+1)S)(4)Pc](2)Lu(III) films were in the range of 2.10(-4)-3.10(-3)%/ppm.

Evaluation of a fast wastewater odour characterisation procedure using a chemical sensor array.

Sewage treatment works are one of the major sources that cause atmospheric odour pollution. The increase in the number of complaints about odour nuisance is due to the increase in environmental concerns. Unfortunately, the legislation on odour nuisance from sewage treatment works is very limited. In order to determine suitable thresholds on which to base legal standards, reliable and efficient odour measurement methods need to be defined. A chemical sensor array was developed for the purpose of measuring wastewater odour. This paper describes the development of the chemical sensor system which is specifically tuned to odours of wastewater origin and which can give an electronic measure of the wastewater odours. Odour emissions from a wastewater treatment facility were detected by using a quartz crystal microbalance (QCM) sensor array. The array consists of nine sensor elements, which were coated with different materials. In this paper, the usage of these novel instruments in the water industry was shown.

Synthesis, Photophysical and Photochemical Properties of a Set of Silicon Phthalocyanines Bearing Anti-Inflammatory Groups

In this study, a series of novel silicon (IV) phthalocyanines conjugated axially with anti-inflammatory (sulindac) and triethylene glycol groups has been synthesized. Different synthetic strategies were attempted to obtain the targeted molecules in high yield. The compounds were fully characterized by using different analyses techniques. Our objectives were to generate a system with sulindac group which enhances the singlet oxygen generation and exhibits anti-cancer effect. Therefore, photophysical and photochemical properties of these compounds were investigated in different solvents. The substituent effect on fluorescence quantum yield and singlet oxygen generation was evaluated for efficiency in photodynamic therapy (PDT) as photosensitizer. The molecules exhibited no aggregation tendency, solubility in common organic solvents, high singlet oxygen quantum yield and high photostability in DMSO so these favourable properties make them good candidates as photosensitizer for PDT. In addition, their stabilities were investigated in DMSO, THF, acetonitrile and DMF.

Liquid crystalline alkylthia-substituted novel phthalocyanines: synthesis and characterization

Methylene-bridged tetra- and octa-alkylthia substituted metal free- and Ni(II) phthalocyanines were synthesized from the corresponding phthalonitrile derivatives in the presence of the anhydrous metal salt (NiCl2) or a strong organic base. The new compounds were fully characterized by elemental analyses, UV-vis, IR, NMR and mass spectra. The mesogenic properties of these materials were studied by differential scanning calorimetry, optical microscopy and X-ray diffraction investigations. X-ray diffraction patterns of the mesophase confirmed that the tetra- and the octa-substituted compounds formed hexagonal columnar mesophases (Colh). The mesogenic properties of these compounds were compared to that of their octa alkythia substituted phthalocyanine derivatives in the literature.

Phthalocyanine-chalcone conjugates

A phthalocyanine-chalcone conjugate was previously reported to retain the full photodynamic activity of the phthalocyanine and a slightly lowered antivascular effect of the chalcone. Assuming that it was due to an insufficient release of the chalcone, we described here several grafting modes applied to the preparation of phthalocyanine-chalcone conjugates.