The Efficiency of the Formation of Singlet Oxygen by a Sensitizer Based on Zinc Phthalocyanine

Using zinc octa(diethoxyphosphenylmethyl)phthalocyanine as an example, we determined experimentally the quantum yield of generation of singlet oxygen () which makes it possible to evaluate quantitatively the efficiency of photogeneration of ¹O₂ and the influence of biomolecules on this parameter. It is shown that the efficiency of generation of singlet oxygen by the sensitizers used in photodynamic therapy depends on their state in a solution and increases with disaggregation of the dye and its interaction with biomolecules. It is established that phthalocyanine in an aqueous buffer solution sensitizes the formation of ¹O₂ with the quantum yield = 0.16 ± 0.02. On introduction of the detergent Triton X100 into the buffer solution of phthalocyanine, increases up to 0.48 ± 0.07. In a microheterogeneous medium (buffer + albumin) = 0.42.     

Effect of Deuteration on Quasiline Electronic‐Vibrational Spectra of Phthalocyanine

Quasiline electronicvibrational spectra of fluorescence and absorption (excitation of fluorescence in selective recording) of the molecules of phthalocyanine deuterated around the periphery of benzene rings (H₂Phcd ₁₆) and the center of the macrocycle (D₂Phc) are obtained. The vibrational frequencies of the ground state are almost insensitive to this deuteration (except for vibrations with the participation of angular deformations). In excitation spectra, changes in deuteration are more pronounced due to the effects of nonadiabatic vibronic interaction of the vibrational sublevels of the S ₁ state and of the purely electronic level S ₂.     

In-situ Synthesis of Copper Phthalocyanine in Silica Xerogel Matrix

Using a newly developed in-situ syntheses technique during sol-gel process, copper phthalocyanine (CuPc) is synthesized in-situ in silica xerogel matrix homogeneously. It has been confirmed by UV-Vis and IR spectroscopies that the copper ions which existed in the form of complex-ions [Cu(H₂O)₄]²⁺ and [CuCl₄]^2– in the stages of sol and wet gel were destroyed in the heat treatment process, meanwhile the copper phthalocyanine molecules were synthesized in-situ gradually during the wet gel to xerogel transition. The dimerization phenomenon of CuPc in the composite is suppressed greatly because the in-situ synthesized CuPc molecules were well isolated in the micro-pores of the xerogel matrix. The doping concentration of Copper phthalocyanine in sol-gel derived matrix can be enhanced also by this in-situ synthesis method.     

Synthesis and characterization of novel flavonoid-substituted phthalocyanines using (±)naringenin

In this study, novel unsymmetrical mono- and di-substituted metal free and metallo phthalocyanines containing peripheral naringeninoxy moieties have been prepared. The naringenin-substituted phthalonitrile was synthesized from 4-nitrophthalonitrile and (±)naringenin in dimethylsulfoxide. Preparation of unsymmetrical mono- and di-substituted phthalocyanines, 2-naringenin-7-O-phthalocyaninatozinc, 2,9-bis-naringenin-7-O-phthalocyaninatozinc, 2,9-bis-naringenin-7-O-phthalocyaninatocobalt and 2,9-bis-naringenin-7-O-phthalocyanine was performed at 120-140 °C using the corresponding phthalonitrile in the presence of N,N-dimethylethanolamine (DMAE), ZnCl₂, CoCl₂ and LiCl, respectively. Synthesized new phthalocyanine compounds have been characterized by elemental analysis and ¹H NMR, ¹³C NMR, FT-IR, MS and UV-vis spectroscopy. These are the first known examples of flavonoid-substituted phthalocyanines.     

Metal-free electrophilic fluorination of alkyl trifluoroborates and boronic acids

Secondary alkyl trifluoroborates undergo facile electrophilic fluorination under mild conditions to afford the corresponding benzylic fluorinated adducts in excellent yield.     

Fabrication of a covalently attached multilayer film electrode containing cobalt phthalocyanine and its application as a potentiometric sensor of iodide ion

Construction of a highly stable covalently attached multilayer film electrode containing cobalt phthalocyanine was achieved by UV irradiation of ionic self-assembled multilayer films of diazo-resins (DAR) and cobalt phthalocyanine tetrasulfonic acid (CoTsPc) tetrasodium salt. The modified electrode had good potentiometric response to iodide ion. The potentiometric response was independent of the pH of the solution between pH 2.5 and 6.0, while it was dependent on the nature of the buffer media. The modified electrode had a linear dynamic range between 4.7×10⁻⁶ M and 0.1 M with a Nernstian slope of 58.8 mV per decade and a detection limit of 3.5×10⁻⁶ M in acetate buffer (0.1 M, pH 4.6). The modified electrode also exhibited a fast response, good stability and repeatability.     

Polymeric complex micelle loaded with axially substituted silicon（IV） phthalocyanine

A novel axially substituted silicon(IV) phthalocyanine, namely di-pyridyloxy axially substituted silicon(IV) phthalocyanine 2 was synthesized and characterized by UV/vis, IR, elemental analysis, MS as well as ¹H NMR spectroscopy. Hydrophobic 2 was encapsulated by amphiphilic triblock copolymer poly[N^ε-(benzyloxycarbonyl-lysine]-poly(ethylene glycol)-poly[N^ε-(benzyl oxycarbonyl) (PLL(Z)-b-PEG-b-PLL(Z)) to form hydrophobic 2-loaded polymeric complex micelle (PIC) (2-loaded PIC). Atom force microscopy (AFM) image showed that 2-loaded PIC formed a spherical nanocarrier with approximately 35-50 nm in diameter. The fluorescence intensity and lifetime of 2-loaded PIC was significantly enhanced by the incorporation 2 into PIC nanocarrier.     

BF3-catalyzed oxidative tandem annulation-aromatization of naphthols with terminal aryl alkenes

A metal-free oxidative arene/alkene annulation-aromatization has been realized, which enables efficient synthesis of 2-arylnaphtho[2,1-b]furans from readily available terminal aryl alkenes and 2-naphthols. Mechanistic study suggests that this reaction proceeds via free-radical initiated tandem cyclization, dehydrogenative rearomatization and aromatization.     

Solvent- and metal-free selective oxidation of thiols to disulfides using I2/DMSO catalytic system

We describe herein a simple, fast and inexpensive protocol for the oxidative coupling of thiols employing a stoichiometric amount of DMSO and iodine as the catalyst. Various aromatic disulfides were obtained in good to excellent yields in short reaction times at room temperature, while aliphatic disulfides were achieved in good yields when the reactions were conducted under microwave irradiation.