FLUORESCENCE SPECTRAL CHANGES OF HEMATOPORPHYRIN DERIVATIVE UPON BINDING TO LIPID VESICLES, Staphylococcus aureus AND Escherichia coli CELLS

Abstract— The binding of hematoporphyrin derivated (Hpd) to lipid vesicles and bacterial membranes was determined by fluorescence spectroscopy. The fluorescence measurements of Hpd in aqueous solutions showed two bands at 613 and 677 nm. In lipid environments of lecithin vesicles the fluorescence spectrum was shifted to 631 and 692 nm, respectively. Hpd was rapidly bound to the cell membrane of Staphylococcus aureus while much less binding occurred in the presence of Escherichia coli. At the same time, spheroplasts of both bacteria were shown to bind Hpd to a similar extent. These results are well correlated with the photoinactivation of the gram positive bacteria with Hpd while the gram negative cells were shown to be resistant. The pH dependence of both Hpd binding to S. aureus as well as the photodynamic inhibitory effect of the same bacteria are similar. It is concluded that the segregation of Hpd to the cell membrane is a prerequisite for its photodynamic effect.     

Ferromagnetism in a dinuclear nickel(II) complex containing triethylenetetramine and tricyanomethanide

Triethylenetetramine (L(4)) was used as a tetradentate blocking ligand that, after complexation with Ni(II), leaves two sites ready for ligation with tricyanomethanide. The formed binuclear complex [L(4)Ni(NCC(CN)CN)(2)NiL(4)](ClO(4))(2) exhibits a ferromagnetic coupling with J/hc = +0.15 cm(-1) and g(Ni) = 2.126; below 16 K, a ferromagnetic ordering is evidenced by ac magnetic susceptibility (both in-phase and out-of-phase), magnetization, field-cooled magnetization, and zero-field-cooled magnetization measurements.     

Novel methyl helianthrones as photosensitizers: synthesis and biological evaluation

A combination of light, oxygen and a photosensitizer is used to induce death of cancer cells by photodynamic therapy. In this study, we have synthesized several new methyl helianthrone derivatives and compared their phototoxicity with that of hypericin. In contrast to hypericin, methyl helianthrones are soluble in aqueous solutions and have a broad range of light absorbance, which allows the use of polychromatic light. Structural modifications of methyl helianthrone demonstrated that substitution of hydrogen atoms of methyl helianthrone at Positions 2 and 5 with Br atoms or methylation of its phenolic hydroxyls, significantly increases the corresponding singlet oxygen quantum yield and their phototoxicity toward alphaT3-1, M2R and LNCaP cells. The phototoxicity of some of these compounds was similar to that of hypericin. Methyl helianthrones, like hypericin, accumulated mainly in the perinuclear region as evident by confocal microscopy. Irradiation of cells pretreated with methyl helianthrone derivatives generates intracellular reactive oxygen species and lipid free radicals, as shown by a fluorescentic probe and electron paramagnetic resonance methods, respectively. The phototoxicity of these methyl helianthrones as well as their ability to oxidize membrane lipids were significantly decreased on addition of specific Type-II inhibitors, suggesting the involvement of singlet oxygen as the main oxidant.     

THE EFFECT OF LIPOSOMES'' MEMBRANE COMPOSITION ON THE BINDING OF THE PHOTOSENSITIZERS HPD AND PHOTOFRIN II

Abstract— Photofrin II (PF-II) is the commercial name of the active photosensitizer which is used in photodynamic therapy of cancer. The effect of the composition of lipid membranes on the binding of PF-II was studied and compared to hematoporphyrin derivative (Hpd), which is a complex mixture of porphyrins and from which PF-II is separated. We find that increasing the content of cholesterol in the bilayer decreases the partitioning of PF-II into the bilayer, similar to what we have found earlier with Hpd. However, inserting DMPC or DPPC into the membrane, which was shown to decrease the binding of Hpd, causes the opposite trend with PF-H. A membrane fluidizer such as benzyl alcohol also has different effects on the membrane binding of Hpd and PF-II. The rate of binding of PF-II to a lipid membrane is about 10 times lower than that of Hpd. These results as well as I^- quenching of the fluorescence of the two porphyrins indicate that PF-II is immersed less homogeneously and deeper in the bilayer than Hpd. The unique additive-dependent binding of PF-II to lipid membranes calls for care in using Hpd as a model photosensitizer.     

Tetragonal low-temperature structure of LiAl

The cubic face-centered structure of LiAl (, at ) transforms into a tetragonal body-centered structure (I4₁/amd, , at ). This first-order phase transition at about during heating is probably the reason for the so-called “ anomalies” in some physical properties like specific heat, electrical resistivity and nuclear-spin lattice relaxation. This transition seems to be correlated with the composition Li:Al of the alloy and the amount of Li vacancies.     

Synthesis, crystal structure and magnetic properties of new indium rhenium and scandium rhenium oxides, In6ReO12 and Sc6ReO12

The new complex indium rhenium and scandium rhenium oxides, In₆ReO₁₂ and Sc₆ReO₁₂, have been synthesized as single phases in sealed silica tubes and by high-pressure high-temperature syntheses, and their crystal structures have been determined by single crystal X-ray diffraction.The compounds crystallize in a rhombohedral structure related to the distorted fluorite structure like Ln₆ReO₁₂ for some rare earth elements, S. G.: R-3, Z=3, a_H= 9.248(2) Å, c_H=8.720(2) Å for Sc₆ReO₁₂ and a_H=9.492(1) Å, c_H=8.933(1) Å for In₆ReO₁₂. A maximum in magnetization is observed for Sc₆ReO₁₂ at T(M_max)=1.89(2) K, whereas ferromagnetic ordering is found for In₆ReO₁₂ by a pronounced increase in the temperature dependence of magnetization at T_C=7.5(5) K. The magnetic moment per rhenium ion in In₆ReO₁₂ and Sc₆ReO₁₂ is 0.84(1) and 0.65(1) μ_B, respectively, derived from the paramagnetic regions.     

Rotational brownian motion and fluorescence intensify fluctuations

A theory, which connects rotational brownian motion with intensity fluctuations of the light emitted from fluorescent molecules excited by linearly polarized light, is given. Analysis of rotational diffusion in this way does not depend on the close relationship between fluorescence lifetime and rotational relaxation times, which is necessary in present methods and thus makes an enlarged time range available for fluorescence spectroscopy.When short fluorescence lifetimes are used the rotational diffusion of the molecule in its ground state will be observed.     

Many-to-many location-routing with inter-hub transport and multi-commodity pickup-and-delivery

In this paper, we consider a variant of the many-to-many location-routing problem, where hub facilities have to be located and customers with either pickup or delivery demands have to be combined in vehicle routes. In addition, several commodities and inter-hub transport processes are taken into account. A practical application of the problem can be found in the timber-trade industry, where companies provide their services using hub-and-spoke networks. We present a mixed-integer linear model for the problem and use CPLEX 12.4 to solve small-scale instances. Furthermore, a multi-start procedure based on a fix-and-optimize scheme and a genetic algorithm are introduced that efficiently construct promising solutions for medium- and large-scale instances. A computational performance analysis shows that the presented methods are suitable for practical application.     

The Effect of Lipid Composition on the Permeability of Fluorescent Markers from Photosensitized Membranes

There is evidence indicating that the cellular locus of PDT action by amphiphilic sensitizers are the cellular membranes. The photosensitization process causes oxidative damage to membrane components that can result in the cell's death. However, it was not yet established whether lipid oxidation can cause free passage of molecules through the membrane and, as a result, be the primary cause of the cell's death. In this work, we studied the effect of liposomes' lipid composition on the kinetics of the leakage of three fluorescent dyes, calcein, carboxyfluorescein and DTAF, which were trapped in the intraliposomal aqueous phase, after photosensitization with the photosensitizer deuteroporphyrin. We found that as the degree of fatty acid unsaturation increased, the photosensitized passage of these molecules through the lipid bilayer increased. We also found that the rate of leakage of these molecules was affected by their size and bulkiness as well as by their net electric charge. In liposomes that are composed of a lipid mixture similar to that of natural membranes, the observed passage of molecules through the membrane is slow. Thus, the photodynamic damage to lipids does not appear to be severe enough to be an immediate, primary cause of cell death in biological photosensitization.