Journal of Porphyrins and Phthalocyanines

Attachment of synthetic analogs of natural tetrapyrroles to electroactive surfaces enables physicochemical interrogation and may provide material for use in catalysis, diagnostics, and energy conversion. Six synthetic zinc chlorins and one free base bacteriochlorin, tailored analogs of chlorophyll and bacteriochlorophyll, respectively, have been attached to Si(100) via a high-temperature (400°C) baking method. The hydroporphyrins bear diverse functional groups that enable surface attachment (vinyl, acetyl, triisopropylsilylethynyl, pentafluorophenyl, and hydroxymethylphenyl) and a geminal dimethyl group in each reduced ring for stabilization toward adventitious dehydrogenation. The films were examined by cyclic voltammetry, FTIR spectroscopy, X-ray photoelectron spectroscopy, and ellipsometry. Monofunctionalized and difunctionalized hydroporphyrins gave monolayer and multilayer films, respectively, indicating robustness of the hydroporphyrin molecules, but in each case the film was more heterogeneous than observed with comparable porphyrins. The data suggest that some amount of unattached molecules remain intercalated with surface-attached molecules. Additional molecular designs will need to be examined to develop a deep understanding of the structure-activity relationship for formation of homogeneous monolayers and multilayers of synthetic hydroporphyrins.

A series of zinc$p$-hydroxylphenylporphyrins was synthesized and characterized by spectroscopic and electrochemical methods in four different nonaqueous solvents. The investigated compounds are represented as [($p$-HOPh)${}_n$(ptBuPh)${{}_{\mathrm{\text{4-}}}}_n$P]Zn, where P represents the dianion of a porphyrin, Ph represents a phenyl group, HO and $t$Bu are para substituents on the meso-phenyl rings of the macrocycle and $n$ = 0–4. The four utilized nonaqueous solvents were dichloromethane (CH${}_{\mathrm{\text{2}}}$Cl${}_{\mathrm{\text{2}}})$, NN-dimethylformamide (DMF), dimethylsulfoxide (DMSO) and pyridine (Py) which were selected on the basis of their coordinating capabilities. The UV-visible spectra and redox potentials of each porphyrin were analyzed both as a function of Hammett substituent constants for groups at the para-positions of the meso-phenyl rings and as a function of the Gutmann solvent donor number which is related to the coordinating ability of the solvent. Each porphyrin exhibits two reductions in CH${}_{\mathrm{\text{2}}}$Cl${}_{\mathrm{\text{2}}}$, DMSO and Py while three reductions are observed in DMF, the additional reaction being due to a phlorin product generated in solution after formation of the porphyrin dianion. Two or three reversible oxidations were seen in CH${}_{\mathrm{\text{2}}}$Cl${}_{\mathrm{\text{2}}}$, the exact number depending upon the specific porphyrin and the presence of $p$-OH substituents at the meso-phenyl rings of the compound. The first two oxidations were assigned as involving the conjugated macrocycle and the third is associated with oxidation of the meso-HOPh group(s).

The most difficult problem on syntheses of the phthalocyanine-based liquid crystals is the long reaction time. In order to shorten the reaction time, we have developed novel Methods A, B and D, for the syntheses of phthalocyanine-based liquid crystals by using microwave heating and/or adding a phase transfer catalysis of Aliquat 336. A series of phthalocyanine derivatives C${}_{\mathrm{\text{n}}}$PcZn(1) ($n=$ 10, 12, 14, 16 and 18: a, b, c and e) could be successfully synthesized in a dramatically short reaction time of 30–60 min using Methods A and B by microwave heating. On the other hand, anothor series of the derivatives C${}_{\mathrm{\text{n}}}$(OH)PcZn (2a–2e) could not be synthesized by microwave heating. Therefore, all these derivatives were synthesized using conventional Method C by oil bath heating, but the reaction took a very long time (22.5–88 h). To shorten the reaction time, we have developed Method D by oil bath heating with adding a phase transfer catalyst of Aliquat 336. In this method, we successfully shortened the reaction time from 88 h to 3 h for the synthesis of the derivative 2a. Thus, the reaction time for oil bath heating can be also greatly shortened by adding the phase transfer catalyst of Aliquat 336. Furthermore, we have established from POM, DSC and temperature-dependent X-ray diffraction measurements that the derivative C${}_{\mathrm{\text{10}}}$PcZn (1a) shows a very rare pseudohexagonal columnar (Col${}_{\mathrm{\text{hr}}})$ phase, and that the derivatives C${}_{\mathrm{\text{n}}}$PcZn (1b–1e) and C${}_{\mathrm{\text{n}}}$(OH)PcZn (2b–2e) exhibit spontaneous perfect homeotropic alignment in a large area between two glass plates in their Col${}_{\mathrm{\text{tet}}}$ phases.

Even though oxypyriporphyrin, a pyridone-containing porphyrinoid system, has the equivalent coordination core to true porphyrins, its coordination chemistry has been little explored. In this study, the first examples of palladium(II), platinum(II) and silver(II) oxypyriporphyrins have been synthesized. Conventional conditions failed to result in the formation of a platinum(II) complex, but moderate yields were obtained when oxypyriporphyrin was reacted with platinum(II) chloride in refluxing mixtures of DMF and acetic acid containing potassium acetate. The palladium(II) and platinum(II) derivatives were characterized by X-ray crystallography. The structurally analogous carbaporphyrinoid system oxybenziporphyrin was also shown to react with platinum(II) chloride under the same conditions to give a platinum(II) hydroxybenziporphyrin complex. Unlike oxybenziporphyrin, this complex is only weakly diatropic. In the presence of base, the diatropic character was reasserted to afford an aromatic anionic species.

The present work reports on the investigation of the possible influence of insulin on the photodynamic effect of the photosensitizer radachlorin on four cell lines: HepG2, HT-29, BJ and BALB/3T3. For a quantitative comparison, the insulin effect on the standard chemotherapy drug methotrexate is also measured. The results show that the EC${}_{\mathrm{\text{50}}}$ value for methotrexate is 40% higher than when combined with insulin; and for the lowest methotrexate concentration used, the difference exceeds 120%. For the case of the photodynamic effect, it is shown that insulin, when applied in combination with radachlorin, improves the cell permeability for the photosensitizer, thus increasing its concentration in the cells. The cytotoxic effect of photodynamic therapy with radachlorin as the photosensitizer has been quantitatively compared. The quantitative comparison of the photodynamic effect in the cases of using the photosensitizer radachlorin both alone and in combination with insulin, shows that the addition of insulin does not have an effect on the model of normal cell lines used; while for the HepG2 tumor cells, a two-fold increase in the EC${}_{\mathrm{\text{50}}}$ value is measured.

In the present study, graphene oxide-supported cobalt (II) tetrasulfophthalocyanine (CoTsPc-GO) was synthesized using the incipient wetness impregnation assisted $\pi$–$\pi$ assembling method. Applications for this material were investigated for ethyl mercaptan, $n$-propyl mercaptan and $n$-butyl mercaptan oxidation from fluid catalytic cracking (FCC) gasoline in a fixed bed reactor. The synthesized CoTsPc-GO catalysts were characterized using UV-vis spectroscopy, Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), Raman spectroscopy analysis, field emission scanning electron microscopy (FESEM), energy dispersive X-ray (EDAX), thermogravimetric and differential thermal analysis (TGA-DTA), inductively coupled plasma optical emission spectroscopy (ICP-OES), and transmission electron microscopy (TEM). The effect of cobalt (II) tetrasulfophthalocyanine (CoTsPc) content (0–0.34 g), catalyst dosage (0.02–0.12 g) and temperature (30–40∘ C) on the performance of CoTsPc-GO catalysts were investigated during the Merox process. The stability and reusability of CoTsPc-GO catalyst for mercaptans oxidation were also tested. The obtained results revealed that the maximum mercaptan oxidation during the Merox process was obtained in CoTsPc-GO of 0.34 g, catalyst content of 0.1 g and a temperature of 40∘ C with ethyl mercaptan, $n$-propyl mercaptan and $n$-butyl mercaptan conversions of 99.9, 98.5 and 97.0%, respectively. The potential of CoTsPc-GO catalyst was investigated for further mercaptans oxidation. The results were compared to those obtained with an industrial impregnated active charcoal catalyst and a CoPc catalyst. The obtained results demonstrated the higher capability of CoTsPc-GO catalyst for mercaptans oxidation from FCC gasoline.

Optical limiting properties of 2,6-dibromo-3,5-distyrylBODIPY dyes were investigated by using the z-scan technique at 532 nm in the nanosecond pulse range. A strong reverse saturable absorption response was observed even in solution, which suggests that compounds of this type are potentially suitable for use in optical limiting applications.

An alternative route to benziporphyrins has been developed. Reaction of an $\alpha$-unsubstituted pyrrole ethyl ester with isophthaloyl chloride in the presence of aluminum chloride afforded a diketone that underwent selective reduction with diborane to give a benzitripyrrane. Cleavage of the ethyl esters with sodium hydroxide in refluxing ethylene glycol, followed by acid catalyzed condensation with a pyrrole dialdehyde and oxidation with DDQ, generated the targeted benziporphyrin product. Spectrophotometric titration of the benziporphyrin with trifluoroacetic acid (TFA) demonstrated the sequential formation of mono- and dicationic species. At lower dilutions, the free base benziporphyrin showed unusually strong ${}^{\mathrm{\text{5}}}{J}_{\mathrm{\text{HH}}}$ coupling between two adjacent methyl substituents, indicating that the connecting unit has substantial olefinic characteristics.

In this study, the monomeric subphthalocyanines bearing azido (2) and terminal ethynyl (3) groups were synthesized. These subphthalocyanines were converted to their dimeric derivatives using azide-alkyne Huisgen cycloaddition and palladium-catalyzed Glaser–Hay coupling reactions subphthalocyanine (4) and (5), respectively. The novel subphthalocyanines were fully characterized by elemental analysis and general spectroscopic methods such as MALDI-TOF mass, FT-IR, UV-vis and ${}^{\mathrm{\text{1}}}$H-NMR. All synthesized subphthalocyanines showed quite good solubility in the most of common organic solvents. The fluorescence measurements were conducted for these subphthalocyanines to estimate their fluorescence quantum yields. The singlet oxygen generation abilities were also examined to investigate their photosensitizer properties.

Silicon (IV) phthalocyanines bearing one or two biotin groups on the axially positions were synthesized, and these novel phthalocyanines were characterized by elemental analysis and standard spectroscopic techniques such as FT-IR, ${}^{\mathrm{\text{1}}}$H NMR, UV-vis and MALDI-TOF. The synthesized compounds are the first examples of axially biotin substituted silicon (IV) phthalocyanines. These phthalocyanines were designed as targeting photosensitizers for the treatment of cancer by photodynamic therapy (PDT) technique. The phthalocyanine ring was selected for its photosensitizer ability and the biotin group was selected as a targeting agent for increasing accumulation of these photosensitizers in tumor cells. The photophysical (fluorescence quantum yields and lifetimes) and photochemical (singlet oxygen generation) properties of the target silicon(IV) phthalocyanines were investigated in DMSO. The photosensitizing efficiency of the studied phthalocyanines was tested against human cervical cancer (HeLa) cells at different photosensitizer concentrations. Both axially mono- and bis-biotin substituted silicon(IV) phthalocyanines present high photocytotoxicity against HeLa cancer cells with the cell survival degree ranging from 13% to 50%. The photosensitivity and the intensity of damage were found to be directly related to the concentration of the used photosensitizers. According to the obtained results, both silicon(IV) phthalocyanine derivatives could be promising as photosensitizers for treatment of cancer by PDT technique.

Fe(III)-complexes of amino-substituted tetraphenylporphyrins obtained from solutions in organic solvents: dichloromethane, ethanol, and dimethyl sulfoxide have been electropolymerized. The solvents’ effects on deposition and surface morphology of the obtained polyporphyrin film have been determined. It is only possible to obtain a polyporphyrin film from DMSO solutions through electrochemical activation of electropolymerization by a superoxide anion radical (O${}_2^{•-})$. The activation effect of the dissolved oxygen becomes evident in porphyrin interaction with the superoxide anion radical (O${}_2^{•}-)$ that is synthesized in DMSO thanks to the quasi-reversible redox process. The size of particles forming the film is lowest when the film is deposited from DMSO and highest when it is deposited from dichloromethane. Therefore, the ratio of polyporphyrin phase grain growth rate to the nucleation rate has the highest value when the film is deposited from dichloromethane. Such films have the most developed surfaces, while those deposited from ethanol are the smoothest. If the film is deposited on an ITO-electrode, the particles forming the surface are a little larger than in the case of deposition on Pt, which is explained by a slower nucleation on the ITO surface. FeClT($m$-NH₂Ph)P-based films obtained from ethanol and dichloromethane have negative photo-EMF values, which indicates that the $n$-type films have semiconductor properties.