Tetrasubstituted copper phthalocyanines : correlation between liquid crystalline properties, films alignment and sensing propertie

Copper phthalocyanines (CuPc) containing alkylthio (-S(CH2)nCH3, n=7 and 15), alkyloxy- (-O(CH2)nCH3, n=7 and 15) and polyoxo (-O(CH2CH2O)3CH3 and -S(CH2CH2O)3CH3) substituents were synthesized and investigated to reveal the effects of substituents type (alkylthio, alkyloxy and polyoxo) and the type of the connecting heteroatom (oxygen or sulphur) on the mesogenic properties, films alignment and sensing behaviour. The liquid crystalline properties of these phthalocyanines were investigated by differential scanning calorimetry, polarizing optical microscopy and X-ray diffraction techniques. The structure and morphology of spun thin films of copper phthalocyanine derivatives were studied by the UV-Vis and Raman spectroscopies as well atomic force microscopy. The sensing properties of CuPc films were studied by the measurement of conductivity change upon interaction with ammonia in the range 10-50 ppm. All investigated films of CuPc derivatives display thermotropic columnar mesomorphism. It was shown that the films with polyoxo- (-O(CH2CH2O)3CH3 and -S(CH2CH2O)3CH3) substituents as well as with alkylthio -S(CH2)nCH3 (n=7) substituents, which are liquid crystalline at room temperature, form ordered films with a random planar alignment of columns. Their films exhibit the better sensor performance with the maximal sensor response for the films of CuPc containing (-S(CH2CH2O)3CH3) substituents

Synthesizing and evaluating the photodynamic efficacy of asymmetric heteroleptic A(7)B type novel lanthanide bis-phthalocyanine complexes

Tuncel, Ozge/0000-0002-0873-133X; Ozcelik, Serdar/0000-0003-2029-0108; ONAL, EMEL/0000-0001-7210-9126In this study heteroleptic A(7)B type novel Lu(iii) and Eu(iii) lanthanide phthalocyanines (LnPc(Pox)[Pc '(AB(3)SH)]) with high extinction coefficients have been synthesized as candidate photosensitizers with reaction yields higher than 33%. The singlet oxygen quantum yields of LuPc(Pox)[Pc '(AB(3)SH)] and EuPc(Pox)[Pc '(AB(3)SH)], respectively, were measured 17% and 1.4% by the direct method in THF. The singlet oxygen quantum yield of LuPc(Pox)[Pc '(AB(3)SH)] in THF is the highest among lutetium(iii) bis-phthalocyanine complexes to date. The photodynamic efficacy of the heteroleptic lanthanide phthalocyanines was evaluated by measuring cell viabilities of A549 and BEAS-2B lung cells, selected to representing in vitro models for testing cancer and normal cells against potential drugs. The cell viabilities demonstrated concentration dependent behavior and were varied by the type of phthalocyanines complexes. Irradiation of the cells for 30 minutes with LED array at 660 nm producing flux of 0.036 J cm(-2) s(-1) increased cell death for LuPcPox-OAc, LuPc(Pox)[Pc '(AB(3)SH)] and ZnPc. The IC50 concentrations of LuPc(Pox)[Pc '(AB(3)SH)] and ZnPc were determined to be below 10 nM for both cell lines, agreeing very well with the singlet oxygen quantum yield measurements. These findings suggest that LuPc(Pox)[Pc '(AB(3)SH)] and particularly LuPcPox-OAc are promising drug candidates enabling lowered dose and shorter irradiation time for photodynamic therapy.Scienti.c and Technological Research Council of Turkey (TUB.ITAK)Turkiye Bilimsel ve Teknolojik Arastirma Kurumu (TUBITAK) [116Z337]We are thankful to the Scienti.c and Technological Research Council of Turkey (TUB.ITAK) for financial support (project number: 116Z337)