CONTENTS

Lithium(I) ion transferred quantitatively to ionic liquid, 1-butyl-3-methylimidazolium hexafl uorophosphate (BMIM⁺PF₆^-), with a water-soluble octabromo porphyrin, 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetrakis (1-methylpyridi nium-4-yl)porphyrin ((H₂(OBTMPyP)⁴⁺), H₂P⁴⁺) with no addition of other anions. The equilibrium constants of LiP³⁺and NaP³⁺ transfers to IL were found to be 10^4.83 and 10^1.31 for K_LiP,ILand K_NaP,IL, respectively. LiP³⁺ transferred selectively in the presence of Na⁺ (K_LiP,IL/K_NaP,IL = 10^3.52) to the IL phase through an ion-exchange mechanism.

A new syntheses of μ-oxo dimeric iron(III)porphyrins from the one-pot metallization of meso-tetraarylporphines in DMF are reported. μ-oxo dimeric iron(III)porphyrin was obtained at the yield of 93% from the reaction of meso-tetraarylporphine with ferrous salt in DMF solvent at pH 8-11. Compared with the other synthetic methods of μ-oxo dimeric iron(III)porphyrin from meso-tetraarylporphines, the one-pot metallization have the higher yields of μ-oxo dimeric iron(III)porphyrins and the simpler and more convenient procedures.

Solvent dependent interaction of tetra-15-crown-5-substituted aluminum phthalocyanine with fluoro- and hydroxy-anions were investigated by the fluorescence and UV-vis spectroscopy.

In the present work, we have designed and synthesized nine cationic porphyrins, and studied the interactions of these porphyrins with different DNA. The experimental results indicate that these porphyrins are capable of effectively inducing/stabilizing both human telomeric and NHE III₁ G-quadruplexes in the presence or absence of metal ions. Furthermore, we have discovered that porphyrins with a stronger stabilizing effect on c-myc G-quadruplexes lead to more pronounced downregulation of the c-myc oncogene in the Hep G2 cell line. Supplementary Material

Two cobalt tetrapyridoporphyrazine complexes were investigated as to their electrochemical, UV-visible and ESR spectroscopic properties as well as their aggregation behavior in non-aqueous media. An overall electron transfer mechanism of both derivatives is proposed.

A mild method for O-alkylation of meso-hydroxyphenylporphyrin has been developed using microwave irradiation. This method is clean and efficient for many substrates and results in significant improvement in reaction yield and in a dramatic decrease in reaction time in comparison to thermal heating.

A series of tetrapyrrolic macrocycles such as porphyrins, phthalocyanines and corroles were found to have inhibitory abilities toward acetylcholinesterase (AChE). Their structure-activity relationship was studied. Several compounds were found to have good inhibitory abilities, which could be developed as potential candidates of AChE inhibitors.

A series of core-modifi ed porphyrins with different chemical structures were evaluated as light-harvesting dyes for dye-sensitized solar cell (DSSC). A short side functional group and a carboxylic acid anchoring group (R₂) led to higher device efficiency. In addition, a thiophenyl group was better than the other substituted phenyl groups at meso positions of core- modified porphyrin (R₁).

Hg₂²⁺ and H₂TSPP^4- can form 2:1 (clusters:porphyrin) and 2:2 complexes, while the 1:1 species may be an intermediate only. The differences between the mercury(I) and the corresponding mercury(II) porphyrins in several aspects can prove that no mercury(II) porphyrins can form due to possible disproportion. However, numeorus similarities suggest that the out-of-plane position of the metal center and the distorted structure of the complexes may be responsible for the common properties, the so-called sitting-atop characteristics.

We have synthesized a series of nobel sandwich type phthalocyanine-based lanthanoid complexes, {[(C₁₂O)₂PhO]₈Pc}₂M. We revealed for the first time in metallomesogens that their clearing points strongly depend on the total spin quantum number (S) of the central rare-earth metal ions. Supplementary Material

The quenching mechanism between TriPyP and BSA was studied by fluorescent method and synchronous fluorescence spectra. In addition, the fluorescence spectra of BSA and the absorption spectra of TriPyP was studied by energy transfer theory. It was investigated that the interaction is static quenching progress and similar to the non-radiation energy transfer. The main type of binding force between TriPyP and BSA was also discussed by calculating thermodynamic function. This system could be considered as a model to gain fundamental insights into drug-protein binding.

The new tetrapyrazinoporphyrazine derivatives containing both flexible (linear) and more rigid (dendritic) groups were synthesized. Their spectral properties were discussed in relation to their chemical structures The synthesized tetrapyrazinoporphyrazine metal complexes were characterized by UV-visible spectroscopy, MALDI-TOF-MS (matrix-assisted laser desorption ionization time-of-flight mass) spectroscopy and ¹H NMR spectroscopy.

Selective methylpheophorbide a exo-ring aminomethylation using bis-(N,N-di methylamino)methane was realized and isomerization of the exo-ring aminomethylation product with rhodochlorin 15-acrylic derivative formation was studied. It has been shown that the action of bis(N,N-dimethylamino)methane in the presence of weak acid is a simple and effective method for synthesis of a new chlorin e₆ derivative with two N,N-dimethylaminomethyl substituents in vinyl group.

The spectral manifestations of the distorted forms of sterically unconstrained metallocomplexes of porphyrin (M = Mg, Zn, Pd, Pt) in rare gas and Shpol'skii matrices at cryogenic temperatures were detected. The distinctly different frequencies of the vibronic transitions have been revealed for planar and distorted forms. The appearance of the out-of-plane modes in the phosphorescence spectra of the Pd- and Pt-porphyrin has been demonstrated.

Binding properties of two water soluble metalloporphyrins, Mn(III)5-CBPyP and Mn(III)TMPyP, in the presence of DNA has been studied at various temperatures by several spectroscopy techniques and viscosity measurement. The thermodynamic data indicate that the process is exothermic, enthalpy- and entropy-driven, suggesting that electrostatic forces play a considerable role in the interaction process.

Manganese tetraphenylporphyrin supported on nano-TiO₂ has been synthesized and structurally characterized. It has been shown to have excellent catalytic activity for the aerobic oxidation of α-pinene. Experimental results showed that this much-enhanced activity could arise from possible co-catalysis between metalloporphyrin and the nano-TiO₂ support.

In this work for first time the polyaniline/TiO₂ nanocomposites were successfully synthesized by catalytic aniline polymerization in the presence of TiO₂ nanoparticles with metalloporphyrin and metallophthalocyanine catalysts. The present study is a very simple and economical method for the preparation of polyaniline/TiO₂ nanocomposites. Characterization of this nanocomposite was done with SEM, TGA, FT-IR and CV.

Cobalt phthalocyanine (CoPc), cobalt tetracarboxy phthalocyanine (CoTCPc) and cobalt octacarboxy phthalocyanine (CoOCPc), when adsorbed onto glassy carbon electrodes, show electrocatalytic activity towards the detection of nitrite, L-cysteine and melatonin, which depends on the number of substituents.

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