Novel phthalocyanines containing resorcinol azo dyes; synthesis, determination of pKa values, antioxidant, antibacterial and anticancer activity

Abstract There are many studies about effects on health of compounds having azo groups in literature. However, anticancer, antimicrobial and antioxidant properties of phthalocyanines containing azo dyes are unknown. Therefore, the new metallophthalocyanines (M: Mn, Co, Zn) substituted with resorcinol azo dyes were synthesized and anticancer, antimicrobial and antioxidant properties investigated. All phthalocyanines were synthesized by the microwave assisted method. The structures were characterized by elemental analysis, 1H NMR, 13C NMR, UV/vis, IR and Mass spectroscopy techniques. The antioxidant capacities were analyzed through radical scavenging of DPPH and chelating ability to ferrous cation. The highest DPPH activity was obtained from compounds (1c and 2c) and the best ferrous ion chelating activity was determined from compound 2. The antibiotic activities were evaluated by disc diffusion method. Compound 2 exhibited antibacterial activity against studied bacteria, but the other compounds had no significant antibacterial effect. Cytotoxicity, apoptotic and necrotic effects were examined on cancer cells MCF-7 and healthy fibroblast cells. Compounds 1, 1a and 2a seem to be proper for the future cancer therapy researches. pKa values were determined by potentiometrically according to the half-neutralization method in N,N-dimethyl formamide. The effect of pH on the electronic absorption spectra of compounds (1, 2, 1c and 2c) was reported. The newly synthesized compounds show positive solvatochromism behavior.

[1]  C. Pannemann,et al.  Electrical characterisation of phthalocyanine-fullerene photovoltaic devices , 2001 .

[2]  A. Lever,et al.  Recent studies in phthalocyanine chemistry , 1986 .

[3]  A. Maleki,et al.  Microwave assisted synthesis of metal-free phthalocyanine and metallophthalocyanines , 2007 .

[4]  A. Yamada,et al.  A Simple Synthesis of 4,5-Disubstituted 1,2-Dicyanobenzenes and 2,3,9,10,16,17,23,24-Octasubstituted Phthalocyanines , 1993 .

[5]  M. Strlič,et al.  Anti- and prooxidative properties of gallic acid in fenton-type systems. , 2002, Journal of agricultural and food chemistry.

[6]  A. D'ascanio,et al.  Phthalocyanine formation using metals in primary alcohols at room temperature , 2000 .

[7]  D. Villemin,et al.  Applications of Microwave in Organic Synthesis: An Improved One-step Synthesis of Metallophthalocyanines and a New Modified Microwave Oven for Dry Reactions † , 2001, Molecules : A Journal of Synthetic Chemistry and Natural Product Chemistry.

[8]  P. Doraiswamy,et al.  Current Status of Metals as Therapeutic Targets in Alzheimer's Disease , 2003, Journal of the American Geriatrics Society.

[9]  M. Abkowitz,et al.  Advances in organic photoconductor technology. , 2010, Chemical reviews.

[10]  E. Ağar,et al.  Synthesis, spectroscopic, and molecular structure characterizations of some azo derivatives of 2-hydroxyacetophenone , 2009 .

[11]  Michael Grätzel,et al.  Efficient near-IR sensitization of nanocrystalline TiO2 films by zinc and aluminum phthalocyanines , 1999 .

[12]  C. Ha,et al.  Syntheses and characterization of soluble phthalocyanine derivatives for organic electroluminescent devices , 2001 .

[13]  K. Binnemans,et al.  Synthesis, spectral and mesomorphic properties of octa-alkoxy substituted phthalocyanine ligands and lanthanide complexes , 2001 .

[14]  A. Gül,et al.  Peripherally tetra-palladated phthalocyanines , 2007 .

[15]  V. Ahsen,et al.  The synthesis and electrochemical behaviour of water soluble manganese phthalocyanines: Anion radical versus Mn(I) species , 2008 .

[16]  P. Erbanová,et al.  Biodegradation of synthetic dyes by Irpex lacteus under various growth conditions , 2004 .

[17]  H. Nakazawa,et al.  Antioxidative and anti-glycation activity of garcinol from Garcinia indica fruit rind. , 2000, Journal of agricultural and food chemistry.

[18]  Michael Hanack,et al.  Conducting Stacked Metallophthalocyanines and Related Compounds , 1994 .

[19]  C. Kappe,et al.  Controlled microwave heating in modern organic synthesis. , 2004, Angewandte Chemie.

[20]  T. Nyokong,et al.  Photochemical and photophysical properties of pentoxy- and naphthaloxy appended magnesium and zinc phthalocyanines , 2005 .

[21]  Xiaobo Liu,et al.  Synthesis and curing behavior of a novel benzoxazine‐based bisphthalonitrile monomer , 2010 .

[22]  V. P. Kulinich,et al.  Synthesis and properties of phthalonitriles with an azo chromophore and related phthalocyanines , 2013, Russian journal of general chemistry.

[23]  M. Hanack,et al.  Phthalocyanines as Active Materials for Optical Limiting , 2001 .

[24]  A. Shaabani.  Synthesis of Metallophthalocyanines under Solvent-free Conditions using Microwave Irradiation , 1998 .

[25]  Y. Gök,et al.  Highly Organosoluble Metal‐Free Phthalocyanines and Metallophthalocyanines: Synthesis and Characterization , 2007 .

[26]  J. Palacios,et al.  Reversible change of the spin state in a manganese phthalocyanine by coordination of CO molecule. , 2012, Physical review letters.

[27]  C. Kantar,et al.  Microwave-assisted synthesis and characterization of phthalocyanines substituted with azo compound containing eugenol moiety , 2011 .

[28]  A. Petit,et al.  Improvement in the synthesis of metallophthalocyanines using microwave irradiation , 2005 .

[29]  M. Nicoli,et al.  Antiradical properties of commercial cognacs assessed by the DPPH(.) test. , 2000, Journal of Agricultural and Food Chemistry.

[30]  P. Riby,et al.  A high-yield microwave heating method for the preparation of (phthalocyaninato)bis(chloro)silicon(IV) , 2001 .

[31]  D. Kalemba,et al.  Antibacterial and antifungal properties of essential oils. , 2003, Current medicinal chemistry.

[32]  T. Dinis,et al.  Action of phenolic derivatives (acetaminophen, salicylate, and 5-aminosalicylate) as inhibitors of membrane lipid peroxidation and as peroxyl radical scavengers. , 1994, Archives of biochemistry and biophysics.

[33]  S. Agathos,et al.  White-rot fungi and their enzymes for the treatment of industrial dye effluents. , 2003, Biotechnology advances.

[34]  Joseph G. Young,et al.  Synthesis and characterization of di-disubstituted phthalocyanines , 1990 .

[35]  J. Pommery,et al.  Antioxidant properties of hydroxy-flavones. , 1996, Free radical biology & medicine.

[36]  A. Gül,et al.  Unsymmetrical phthalocyanines with cyclopalladated azo functions , 2012 .

[37]  T. Nyokong,et al.  The effects of carbon nanotubes on the electrocatalysis of hydrogen peroxide by metallo-phthalocyanines. , 2011, Talanta.

[38]  M. S. Blois,et al.  Antioxidant Determinations by the Use of a Stable Free Radical , 1958, Nature.