title: Synthesis and photodynamic properties of adamantylethoxy Zn(II) phthalocyanine derivatives in different media and in human red blood cells.
abstract: Novel unsymmetrically substituted Zn(II) phthalocyanine bearing an adamantylethoxy group (AZnPc) was synthesized by the ring expansion reaction of boron(III) subphthalocyanine chloride with an appropriated phthalonitrile derivative (APc). Also, APc was used to obtain a new Zn(II) phthalocyanine bearing four adamantylethoxy groups (A(4)ZnPc) by cyclotetramerization reaction. The spectroscopic and photodynamic properties of these photosensitizers were compared with those of a Zn(II) phthalocyanine substituted by four methoxy groups (M(4)ZnPc) in different media. Similar results were obtained in N,N-dimethylformamide. However, a higher photodynamic activity was found for AZnPc in a biomimetic system formed by reverse micelles. This behavior was also observed in the presence of human red blood (HRB) cells, which were used as an in vitro cellular model. Thus, AZnPc was the most effective photosensitizer to produce HRB cells hemolysis. The photodynamic effect produced a decrease in the HRB cells osmotic stability leading to the release of hemoglobin. Studies of photodynamic action mechanism showed that photohemolysis of HRB cells was protected in the presence of azide ion, while the addition of mannitol produced a negligible effect on the cellular photodamage, indicating the intermediacy of O(2)((1)Δ(g)). Therefore, the presence of an adamantyl unit in the phthalocyanine macrocycle represents an interesting molecular architecture for potential phototherapeutic agents.
authors.affiliation: Departamento de Química, Facultad de Ciencias Exactas Físico-Químicas y Naturales, Universidad Nacional de Río Cuarto, Agencia Postal Nro. 3, X5804BYA Río Cuarto, Córdoba, Argentina.
authors.forename: A Laura
authors.initials: AL
authors.lastname: Ochoa
authors.forename: Tomas C
authors.initials: TC
authors.lastname: Tempesti
authors.forename: Mariana B
authors.initials: MB
authors.lastname: Spesia
authors.forename: M Elisa
authors.initials: ME
authors.lastname: Milanesio
authors.forename: Edgardo N
authors.initials: EN
authors.lastname: Durantini
mesh_terms: D056831:Coordination Complexes / Q000138:chemical synthesis* / Q000494:pharmacology*; D004912:Erythrocytes / Q000187:drug effects*; D006461:Hemolysis / Q000187:drug effects*; D006801:Humans; D007211:Indoles / Q000138:chemical synthesis* / Q000494:pharmacology*; D008027:Light; D008353:Mannitol / Q000737:chemistry; D008823:Micelles; D015394:Molecular Structure; D017319:Photosensitizing Agents / Q000138:chemical synthesis* / Q000494:pharmacology*; D013329:Structure-Activity Relationship
chemical_list: D056831:Coordination Complexes; D007211:Indoles; D008823:Micelles; D017319:Photosensitizing Agents; C573629:zinc(II) 2-(2-(1-adamantyl)ethoxy)phthalocyanine; D008353:Mannitol