Journal of Porphyrins and Phthalocyanines

A series of different metal centered 5,15-Bis(4-aminophenyl)-10,20-bis(4-bromophenyl)porphyrins (PorM) where M = H₂, MnOAc, FeCl, Co or Zn were synthesized, and then encapsulated in zeolite imidazole framework-8 (ZIF-8) by typical template directed strategy to generate PorM@ZIF-8 metal organic frameworks (MOFs). These composites were characterized by UV-vis, FTIR, XRD, FESEM and HRTEM methods. Each prepared PorM@ZIF-8 MOF retained the molecular structure of porphyrin and crystal structure of ZIF-8. It is clearly shown that porphyrin centered metal ions will affect MOFs morphology. Both PorH₂@ZIF-8 and PorZn@ZIF-8 gave a rhombic dodecahedron, PorMnOAc@ZIF-8 gave a truncated hexagonal prism-like structure, while no specific structures were obtained for PorFeCl@ZIF-8 and PorCo@ZIF-8 due to aggregation as characterized by FESEM spectrum. Oxygen reduction catalytic ability of ZIF-8, PorM and PorM@ZIF-8 were measured in alkaline condition (0.1 M KOH) with the number of electrons transferred being $n$ = 2.20–2.60 and generating HO${}_2^{-}$ as the oxygen reduction product. The catalytic property slightly increased after the porphyrin was encapsulated, due possibly to the capacity limit, inappropriate molecular distance or the direction of encapsulated porphyrin molecular.

In this study, two SiPcs have been selected and the photodynamic therapy potentials were evaluated of the Pcs. Synthesis of Axially 2-decyn-1-oxy disubstituted Es-SiPc-2 was newly synthesized by the reaction of SiPcCl₂ with 2-decyn-1-ol in the presence of NaH in toluene. Furthermore, their nuclear imaging potentials were evaluated in human colon adenocarcinoma (HT-29) and human lung fibroblast cell (WI-38) cell lines. The uptake results have indicated that Es-SiPc labeled with ${}^{131}$I radionuclide (${}^{131}$I-Es-SiPc) was approximately 2-fold higher in the HT-29 cell line than the WI-38 cell line. In other words, the target/non-target tissue ratio is defined as two in the HT-29/WI-38 cell lines. Besides, the uptake values of ${}^{131}$I-Es-SiPc were found to be higher than ${}^{131}$I-Es-SiPc-2. ${}^{131}$I-Es-SiPc and ${}^{131}$I-Es-SiPc-2 are promising for imaging or treating colon adenocarcinoma. In vitrophotodynamic therapy (PDT) studies have shown that both compounds are suitable and can be used in this field. Also, Es-SiPc has been shown to have higher phototoxicity than Es-SiPc-2.

A single crystal of (5,10,15,20-tetraphenylporphyrinato)-silver was obtained and its structure reported. Using direct growth on quartz substrates method, a crystal thin film was obtained and the film’s morphology was investigated by atomic force microscopy. The nonlinear absorption properties of the film were studied using open aperture $Z$-scan technique by picosecond laser pulses at different fluence at wavelength 532 nm, nonlinear saturable absorption behavior was observed. Time-dependent unrestricted Hartree-Fock with the basis set LanL2DZ was used in computing the linear and non-linear optical properties of (5,10,15,20-tetraphenylporphyrinato)-silver.

Co(II) porphyrins have been utilized as efficient and selective catalysts for the extractive oxidative desulfurization reaction on the refractory dibenzothiophene (DBT) in $n$-dodecane (model middle distillate fuel oil). The acetonitrile was taken as extracting polar solvent and H₂O₂ was used as oxidant. The reaction optimization was done with respect to DBT:catalyst molar ratio; DBT:H₂O₂ molar ratio; extracting solvent: CH₃CN/$n$-dodecane volume ratio; reaction temperature and time. Under the optimized conditions, a maximum of $\sim$98% DBT removal was achieved by using the meso-tetrakis(4$\prime$ methoxyphenyl)porphyrinatocobalt(II) as catalyst under mild conditions at 50${}^{\circ }$C.

The [3 + 2]-cycloaddition reaction of various azides with ferrocenylmethylpropargyl ester in the presence of copper (I) salt lead to the formation of ferrocenyl-containing derivatives, including porphyrin, which exhibit pronounced cytotoxicity against Escherichia coli under ultrasound irradiation.

The d/l-enantiomers of a series of three Zn(II)tetraarylporphyrin dimers were synthesized and isolated by incorporating a bridging amide-bonded xanthene moiety at the para-position of one of the meso-aryl rings. The electronic structures and optical properties were modulated by incorporating chiral amino acid moieties into the amide-bonding moieties of the xanthene bridge that contain methyl, tolyl and 2-methylindole substituents. A cofacial dimer was formed in the presence of 1,4-diazabicyclo[2.2.2]octane (DABCO) resulting in a significant red shift of the B band, due to a relative destabilization of the HOMO, which has large MO coefficients on the pyrrole nitrogens. The sign sequences observed in the B band region of the CD spectra due to the presence of the chiral amino acid moieties were modified due to this change in geometry. Significant CD intensity is also observed in the B band region of the CD spectra of anion radical species during in situ spectroelectrochemical measurements.

Mono- and disubstituted 2,6-dibromo-dimethylaminophenylbuta-1,3-dienylBODIPY dyes were successfully prepared, and their in vitro photodynamic activities against MCF-7 breast cancer cells were evaluated with a Thorlabs M660L4 660 nm LED (336 J · cm${}^{-2})$. The IC${}_{50}$ value of the monophenylbuta-1,3-dienylBODIPY was ca. 2.1 $\mu$M, while that of the diphenylbuta-1,3-dienylBODIPY was > 50 $\mu$M. Both dyes exhibited minimal dark toxicity. The results demonstrate that monosubstituted 2,6-dibromo-dimethylaminophenylbuta-1,3-dienylBODIPY dyes merit further in-depth study for use as photosensitizer dyes in photodynamic therapy.

A new zinc phthalocyanine–benzoquinone rigid dyad, QnZnPc–G${}_2$ was synthesized as a model compound to study photo-induced charge separation mimicking natural photosynthesis. Compared to its previously reported analog, this dyad has an additional fused benzene ring between the zinc phthalocyanine (ZnPc) (donor) and benzoquinone (acceptor) moieties. The rigid structure of QnZnPc–G${}_2$ ($i.e.$ no rotamers) is designed to minimize the unusual electronic perturbation induced by the internal motions, which resulted in a significant increase in the lifetime of the charged separated state (from 40 ps to 252 ps). Physical and photochemical properties of this new dyad were examined and discussed in this paper.

Tetra substituted peripheral and non-peripheral Zn(II) phthalocyanines were successfully synthesized employing 4-(bis(3-methyl-1H-indol-2-yl)methyl)phenol as a starting material. The structure of these synthesized compounds was confirmed using ¹H NMR, ${}^{13}$C NMR, infrared (IR), UV-vis, and MALDI-TOF spectral data. The photophysical (fluorescence quantum yields and lifetimes) and photochemical (singlet oxygen generation) properties of all synthesized peripheral and non-peripheral compounds were investigated in order to determine the potential of these compounds for application in photodynamic therapy.