Liposomes characterized by membranes featuring diverse fluidity (liquid-crystalline and/or gel phase), prepared from egg yolk lecithin (EYL) and dipalmitoylphosphatidylcholine (DPPC), were doped with selected metalloporphyrins and the time-related structural and dynamic changes within the lipid double layer were investigated. Porphyrin complexes of Mg(II), Mn(III), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), and the metal-free base were embedded into the particular liposome systems and tested for 350 h at 24°C using the electron spin resonance (ESR) spin probe technique. 5-DOXYL, 12-DOXYL, and 16-DOXYL stearic acid methyl ester spin labels were applied to explore the interior of the lipid bilayer. Only the 16-DOXYL spin probe detected evident structural changes inside the lipid system due to porphyrin intercalation. Fluidity of the lipid system and the type of the porphyrin complex introduced significantly affected the intermolecular interactions, which in certain cases may result in self-assembly of metalloporphyrin molecules within the liposome membrane, reflected in the presence of new lines in the relevant ESR spectra. The most pronounced time-related effects were demonstrated by the EYL liposomes (liquid-crystalline phase) when doped with Mg and Co porphyrins, whereas practically no spectral changes were revealed for the metal-free base and both the Ni and Zn dopants. ESR spectra of the porphyrin-doped gel phase of DPPC liposomes did not show any extra lines; however, they indicated the formation of a more rigid lipid medium. Electronic configuration of the porphyrin’s metal center appeared crucial to the degree of molecular reorganization within the phospholipid bilayer system.Electronic supplementary materialThe online version of this article (doi:10.1007/s00775-010-0715-1) contains supplementary material, which is available to authorized users.
Kinetic studies of photochemical reactions induced by UV radiation in solutions of metal phthalocyanines have been carried out to determine the factors which might have influenced the stability of photosensitized phthalocyanines. Complexes of the molecular type Mpc, M'(2)pc, and Lnpc(2) (where M = Li, Mg, Fe, Co, Zn, Pb; M'= Tl; Ln = rare earth; pc = phthalocyanine ligand, C(32)H(16)N(8)(2-)) were investigated in DMF, DMSO, and pyridine. Progressive decay of the phthalocyanine macrocycle due to absorption of UV light was observed. Phthalimide found in the final photolysis product may indicate some chemically bonded oxygen involved in the solid phthalocyanine material. Fluorescence lifetimes determined for the studied compounds (2.91-5.98 ns) have shown no particular relation to the stability of the excited macrocyclic system. The bonding strength of the photosensitized phthalocyanine moiety appears to rely on typical chemical factors, rather than on the properties of the excited states. Kinetics of the degradation process has proved to depend on the molecular structure of the complex and seems to be controlled by interactions of the macrocycle bridging nitrogen atoms with the solvent molecules. The use of electron acceptor solvents such as DMSO may enhance the molecular stability of phthalocyanines excited by UV radiation. Sandwich-type rare earth diphthalocyanines dissolved in DMSO displayed the highest photostability.
The effect of methanol, ethanol, acetone, N,N-dimethylformamide (DMF), dimethyl sulfoxide and Nujol on the growth of Escherichia coli DH5α, Bacillus subtilis and Saccharomyces cerevisiae D273 was investigated. All of the tested cultures appeared susceptible to the organic media they were treated with, which evinced in apparent hindering of cell development. The observed diverse solvent tolerance, except from their different biochemical activity, may also be related to the changes in cell membrane fluidity induced by the solvent species. Parallel electron paramagnetic resonance investigations using egg yolk lecithin model liposomes revealed that the fluidity of the phospholipid system in cell membranes may either be considerably decreased (Nujol, DMF, ethanol) or increased (acetone), thus rendering difficult the intracellular nutrient supply. Hence, even the chemically neutral Nujol produced a distinct cell-growth inhibitory effect. These results are fairly consistent with the outcome of the survival tests, particularly for the bacteria strains.
The photocatalytic activity of polycrystalline TiO2 samples impregnated with rare-earth-metal diphthalocyanines
was investigated. The 4-nitrophenol (4-NP) photocatalytic degradation in aqueous suspension was used as a
probe reaction. Commercial anatase TiO2 was impregnated with home-prepared double-decker phthalocyanine
complexes of the lanthanide metals, such as Ce, Pr, Nd, Sm, Ho, and Gd. In particular, the impregnation with
Ho, Sm, and Nd complexes, acting as sensitizers, proved beneficial for the photoactivity of the studied systems.
Significant improvements of the TiO2-based catalytic system appeared possible in terms of lower impregnation
loading, enhanced photoreactivity under solar light irradiation, as well as chemical, thermal, and photochemical
stability of the sensitizers. Enhanced photocatalytic activity of TiO2 samples impregnated with lanthanide
diphthalocyanines in comparison with those impregnated with Cu(II)−porphyrin has been manifested in the
decomposition rate of 4-NP. The phthalocyanine sensitizers proved somewhat less efficient for the disappearance
of total organic carbon (TOC).
Structural parameters of a range of over 100 meso-substituted zinc porphyrins were reviewed and compared to show how far the nature of the functional group may affect the interatomic distances and bond angles within the porphyrin core. It was proved that even despite evident deformations of the molecular structure, involving twisting of the porphyrin's central plane, the coupled π-bonding system remains flexible and stable. DFT calculations were applied to a number of selected porphyrins representative for the reviewed compounds to emphasize the relevance of theoretical methods in structural investigations of complex macrocyclic molecular systems. Experimental and DFT-simulated IR spectral data were reported and analyzed in context of the individual molecular features introduced by the meso substituents into the porphyrin moiety base. Raw experimental spectral data, including 1H- and 13C-NMR, UV-Vis, FTIR, XRD, and other relevant physicochemical details have been provided for a specially chosen reference zinc porphyrin functionalized by tert-butylphenyl groups.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.