Distinctively-shaped organosiloxane polymers and composites and phthalocyanines as photosensitizers for photodynamic therapy.

摘要

The synthesis and characterization of 38 organosiloxysiloxane apophyllite-derived sheet polymers, 17 organosiloxysiloxane magadiite-derived sheet polymers, 9 organosiloxysiloxane kenyaite-derived sheet polymers, 1 organosiloxysiloxane silinaite-derived sheet polymer and 7 organosiloxysiloxane K₂CuSi ₄O₁₀-derived tube polymers are described. Ten of the organosiloxysiloxane apophyllite-derived sheet polymers are processable. Typical of these is apophyllite-derived 3-cyanopropyl-dimethylsiloxy sheet polymer, [((NCC₃H₆)(CH ₃)₂SiO)_x(HO)_1−xSiO_1.5] _n, A-CM₂. The processable sheet organosiloxysiloxane polymers can be formed into gels, coatings, films and objects. The sheet organosiloxysiloxane polymers were made by the silylation of sheet silicates or by elaboration reactions on the pendent groups of organosiloxysiloxane sheet polymers. The sheet silicates used were apophyllite (KCa₄Si₈O ₂₀(F,OH)·8H₂O), magadiite (Na₂Si₁₄ O₂₉·7H₂O), kenyaite (Na₂Si ₂₂O₄₅·9H₂O), and silinaite (NaLiSi ₂O₅·2H₂O), while the tube silicate used was K₂CuSi₄O₁₀. The silylation reagents used include monochlorosilanes, dichlorosilanes, trichlorosilanes and mixtures of chlorosilanes. The elaboration reactions include hydrosilylation, alkoxylation and silylation of reactive pendent groups on sheet polymers. The preparation of 9 siloxane-matrix sheet-polymer nanocomposites is also described. In 8 of these, the sheets are fully exfoliated.; In addition, 14 new silicon phthalocyanines designed for use as photosensitizers in photodynamic therapy studies have been prepared and characterized. These 14 photosensitizers are: HOSiPcOSi(CH₃)₂(CH₂) ₄N(C₂H₄)₂ NCH₃, Pc 44; SiPc(OSi(CH ₃)₂(CH₂)₄N(C₂H₄) ₂NCH₃)₂, Pc 45; HOSiPcOSi(CH₃) ₂ (CH₂)₃N(C₂H₄)₂NC ₂H₅, Pc 46; SiPc(OSi(CH₃)₂(CH ₂)₃N(C₂H₄)₂NC₂H ₅)₂, Pc 47; HOSiPcOSi(CH₃)₂(CH ₂)₃N(C₂H₄)(C₃H₆)NCH ₃, Pc 48; SiPc(OSi(CH₃)₂(CH₂) ₃ N(C₂H₄)(C₃H₆)NCH ₃)₂, Pc 49; HOSiPcOSi(CH₃)₂(CH ₂)₃N(CH₂)(C₃H₆)NCH ₃, Pc 50; SiPc(OSi(CH₃)₂(CH₂) ₃N(CH₂)(C₃H₆)NCH₃) ₂, Pc 51; HOSiPeOSi(CH₃)₂(CH₂) ₄ N(CH₂)(C₃H₆)NCH₃, Pc 52; HOSiPcOSi(CH₃)₂(CH₂)₄N(C ₂H₄)₂NC₂H₅, Pc 53; SiPc(OSi(CH ₃)₂(CH₂)₄N(C₂H₄) ₂NC₂H₅)₂, Pc 54; SiPc(OSi(CH₃ )₂(CH₂)₄N(CH₂) (C₃ H₆)NCH₃)₂, Pc 55; SiPc(OSi(CH ₃)₂(CH₂)₃N(C₂H₄) ₂NCH₃)(OSi(CH₃)₂(CH₂) ₃N (C₂H₅)₂), Pc 39; SiPc(OSi(CH ₃)₂(