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[Some spectrum methods on the structures of metal phthalocyanine].

The recent progress in some spectrum methods on the structures of metal phthalocyanine was introduced. IR and UV/Vis spectral properties of phthalocyanine were presented systematically, especially the effect of the types, numbers and positions of the peripheral substituted groups as well as the different aggregation states in solution on the UV/Vis spectra, the characterization method of the isomers of tetra-substituted metal-phthalocyanine by NMR was also discussed.

Indoles↗

Sr3ZnPtO6 and Sr3CdPtO6.

The flux synthesis of single crystals of the isostructural compounds tristrontium zinc platinum hexaoxide, Sr(3)ZnPtO(6), and tristrontium cadmium platinum hexaoxide, Sr(3)CdPtO(6), is reported. The compounds adopt the pseudo-one-dimensional rhombohedral K(4)CdCl(6) structure type, and feature chains of face-shared distorted ZnO(6) or CdO(6) trigonal prisms and PtO(6) octahedra, surrounded by columns of Sr(2+) ions. All transition metals are located on the threefold axis of symmetry, while the Sr(2+) cations lie on twofold axes.

Journal Article↗

Effect of divalent metal ions on DNA studied by capillary electrophoresis.

Divalent metal ions, such as Zn(2+), Co(2+), and Ni(2+), are capable of incorporating into DNA under certain conditions to form complexes termed M-DNA. To better understand the effects of these cations on DNA we used capillary electrophoresis (CE). The presence of these metal ions in a typical genotyping buffer led to broad peaks with low fluorescence intensities. In addition, some of the metal-complexed DNA molecules had different electrophoretic mobilities than their normal DNA counterparts. It is likely that the mobility shifts observed in the electropherograms of these affected fragments are due to the divalent cations causing structural changes in the single-stranded DNA. However, as can be seen from the resulting peak shapes, the structure, charge, and/or mass changes due to metal binding are not conserved among all of the DNA fragments. The extent of both peak-broadening and mobility shifts were found to be dependent on the metal cation and its concentration, the length of time that the DNA sample existed in formamide prior to injection into the capillary, and also the fragment size and sequence. These results suggest that the presence of metal ions might be responsible for the poor CE performance that occurs when genotyping certain kinds of DNA samples.

Cations, Divalent↗

Desorption/ionization on porous silicon mass spectrometry (DIOS) of model cationized fatty acids.

Desorption/ionization on porous silicon (DIOS) is a very useful technique in the case of small molecular weight compounds, compared to the matrix-assisted laser desorption ionization (MALDI). This is because MALDI generates matrix-related ions that overlap with the mass range of interest. The aim of our work was to investigate the suitability of the DIOS technique in the case of fatty acids in negative ion mode. The analysis of the chosen fatty acid models, nonadecanoic acid (C(19)H(38)O(2)) and heneicosanoic acid (C(21)H(42)O(2)), gave rise to the observation of the deprotonated monomeric species and selective cationized multimeric species. This cation selectivity was further elucidated by complementary studies based on the addition of various metals such as Ag(I), Zn(II), Fe(II), and also Cu(II). Specific behavior, depending upon the introduced metal, was highlighted by different redox reaction processes and also metastable decompositions (in PSD mode).

Acetates↗

Photofrin II sensitized modifications of ion transport across the plasma membrane of an epithelial cell line: I. Electrical measurements at the whole-cell level.

Photofrin II is a photosensitizer frequently applied in photodynamic therapy. Light-induced tumor cell inactivation observed in the presence of this substance has been suggested to start with modifications at the level of cellular membranes. In the present study electrophysiological techniques are applied in order to investigate the action of photofrin II on functional properties of the plasma membrane of opossum kidney (OK) cells (as an epithelial model system) and of fibroblasts. Illumination of the cells in the presence of photofrin II (or Zn-phthalocyanine) leads to comparatively fast depolarization of the membrane potential. It is caused by a strong change of the membrane conductance which proceeds in two phases. Both phases contribute to a loss of ion selectivity of the plasma membrane between K+ and Na+. In the first phase, specific pathways for K+, which determine the resting potential under physiological conditions, are inactivated. The second phase is distinguished by a marked increase of a nonselective conductance. The increase of the latter - after light-induced initiation - continues in the dark. The conclusions are derived from light-induced, time-dependent changes of the membrane conductance and of the shape of the current-voltage relationship detected under different experimental conditions.

Animals↗

Entamoeba histolytica: an ecto-phosphatase activity regulated by oxidation-reduction reactions.

In this work, an ecto-phosphatase activity of Entamoeba histolytica was characterized using intact cells. This activity presented the following biochemical characteristics: (i) it hydrolyzes p-NPP with V(max) of 8.00+/-0.22 nmol p-NP x h(-1) x 10(-5) cells and K(m) of 2.68+/-0.25 mM; (ii) it is inhibited by acid phosphatase inhibitors, such as sodium molybdate (K(i)=1.70+/-0.24 microM) and sodium fluoride (K(i)=0.25+/-0.02 mM); (iii) it also showed high sensitivity to phosphotyrosine phosphatase inhibitors, such as sodium orthovanadate (K(i)=1.07+/-0.14 microM), bpV-PHEN (K(i)=0.38+/-0.02 microM) and mpV-PIC (K(i)=0.39+/-0.04 microM). Zn(2+), an oxidizing agent, decreased the enzymatic activity in 50%. DTT and GSH, two reducing agents, enhanced the activity twofold. The non-invasive E. histolytica and free-living E. moshkovskii were less efficient in hydrolyzing p-NPP than the pathogenic E. histolytica suggesting that this enzyme could represent a virulence marker for this cell.

Animals↗

Uptake of Cd, Zn and Mn by willow increases during terrestrialisation of initially ponded polluted sediments.

Metal concentration of plants growing on contaminated soils among other factors may depend on changes in the hydrological regime of the soil. Foliar and stem metal concentrations in Salix cinerea (grey sallow) were measured in 2 consecutive growing seasons on a submerged sediment-derived soil that underwent gradual terrestrialisation. Foliar and stem cutting concentrations for Cd, Zn and Mn increased on plots that were submerged during the first year, but emerged in the second year of monitoring. The litter layer was sampled under the shrubs of a plot with a recent abrupt change in hydrological regime and on the reference plot. It was separated in three size fractions through sieving. Analysis of the litter fractions suggested that Cd and Zn concentrations remained constant during fragmentation. However, Cr, Cu, Ni and Pb concentrations increased, which was attributed to adhesion of mineral soil particles on the fine fraction. After correction for the metal content in the mineral fraction, an increase in Cd, Mn and Cu concentration during fragmentation of the organic part of the litter layer was observed for the polluted plot. Net litter layer decomposition rate was low, which may indicate low colonisation by the decomposing community. Terrestrialisation resulted in higher Cd, Mn and Zn uptake by willows. The deviant litter layer metal concentrations for Cd, Zn and Mn and low decomposition rate must be further monitored. Feasibility of measures aiming at re-establishing wetland conditions for the dredged sediment landfill must be considered.

Belgium↗

Liposome-delivered 131I-labelled Zn(II)-phthalocyanine as a radiodiagnostic agent for tumours.

131I-Zn(II)-phthalocyanine (ZnPc) incorporated into unilamellar liposomes has been systemically injected to mice bearing a transplanted MS-2 fibrosarcoma. Biodistribution studies show that the pharmacokinetic behaviour of 131I-ZnPc is very similar to that defined for the parent molecule ZnPc including a serum half-life of ca. 12 h, a high recovery from liver and spleen and minimal accumulation in kidney and brain. The most important pharmacokinetic parameter is represented by the high tumour/ muscle ratio of 131I-ZnPc concentration (ca. 9 at 24 h post-injection). These results suggest the possible use of the radiolabelled derivative for a real-time non-invasive monitoring of the ZnPc concentration in the tumour and peritumoural tissue during photodynamic therapy.

Animals↗

Photodynamic effect on cancer cells influenced by electromagnetic fields.

The synergism of low-frequency electromagnetic field treatment and photodynamic effect on killing of human cancer cells is presented. The weak pulsating electromagnetic field (PEMF) generated by Helmholtz coils in the mT range influences the permeability of cell membranes for photosensitizers. Several types of sensitizers were excited by visible light during incorporation without and with two kinds of PEMF treatment. In the first part suitable photosensitizers were selected in the absorption range between 400 and 700 nm against human myeloid leukaemia K562 and human histiocytic lymphoma U937 cells by treatment of PEMF consisting of rectangular pulse groups. In the second part amplitude and frequency dependencies were measured using sinuous PEMF and white light with the result that after 12 min the PEMF treatment enhanced photodynamic effectivity by more than 40% over the control value. Taking into account the influence of many parameters, an additional optimization will be possible by photodynamic PEMF synergism for an increased drug delivery in general.

Cell Membrane Permeability↗

Low-density lipoprotein receptors in the uptake of tumour photosensitizers by human and rat transformed fibroblasts.

Low-density lipoproteins (LDL) increase the selectivity of tumour targeting by drugs, including sensitisers for photodynamic therapy, because of the enhanced expression of specific LDL receptors in many types of transformed as compared with non-transformed cells. This investigation aims at gaining more information on the role of LDL receptors in the accumulation of photosensitizer-LDL complexes by human and rat transformed fibroblasts, and the interference of the photosensitizer with LDL recognition by the specific receptors. Both an amphiphilic hematoporphyrin IX (Hp) and a hydrophobic Zn(II)-phthalocyanine (ZnPc) photosensitizers bind to human LDL with molar ratios of 5-6:1 and 10-12:1, respectively. The hematoporphyrin-LDL complex is accumulated by human HT1080 fibroblasts mainly through the high affinity LDL receptors, while the Zn-phthalocyanine-LDL complex is internalised through non specific endocytosis because of changes in the apoB LDL structure induced by phthalocyanine association, as suggested by spectroscopic studies. The uptake of LDL-delivered hematoporphyrin, but not Zn-phthalocyanine, is about 4-fold higher in HT1080 cells stimulated for maximal expression of LDL receptors as compared with non-stimulated cells. This difference is abolished by LDL acetylation. Human LDL-bound hematoporphyrin and Zn-phthalocyanine are up taken by stimulated and non-stimulated 4R rat fibroblasts with similar efficiency. Scatchard plot analysis of human (125)I-LDL binding to 4R cells shows the presence of only low affinity receptors while 350,000 high affinity receptors are expressed per HT1080 cell. It is concluded that a careful evaluation of the lack of conformational changes of LDL is critical for guaranteeing the selectivity and efficiency of photosensitizer delivery to tumour cells.

Animals↗

Photoreductive dehalogenation of halogenated benzene derivatives using ZnS or CdS nanocrystallites as photocatalysts.

ZnS nanocrystallites (nc-ZnS) prepared in N,N-dimethylformamide (DMF) photocatalyze dehalogenation of halogenated benzenes to benzene as the final product from chlorinated benzenes and to difluorobenzenes from fluorinated benzenes in the presence of triethylamine (TEA) as an electron donor under UV light irradiation (lambda > 300 nm). When CdS nanocrystallites (nc-CdS) are used as a photocatalyst (lambda > 400 nm), halogenated benzenes are photoreductively dehalogenated, yielding trichlorobenzene from hexachlorobenzene and tetrafluorobenzene isomers from hexafluorobenzene as the final products. Photoformed electrons on nc-ZnS and nc-CdS have such negative reduction potentials that these electrons reduce polyhalogenated benzenes, leading to the successive dehalogenation. nc-ZnS exhibits higher photocatalytic activitythan nc-CdS due to the more negative potential of the electrons on nc-ZnS than that on nc-CdS. The higher activities of nc-ZnS and nc-CdS compared to their bulk forms are explained as being due to their quantum size effects and the adsorptive interaction between the substrates and the nanosized photocatalysts.

Benzene Derivatives↗

Preparation of nanosized ZnS-passivated CdS particle films via the MOCVD process with co-fed single source precursors.

A novel approach was developed to prepare thin films of nanosized ZnS-passivated CdS particles via a metal-organic chemical vapor deposition (MOCVD) process with co-fed single source precursors of CdS and ZnS. Single source precursors of CdS and ZnS with sufficiently different reactivity, as judged from thermogravimetry analysis, were prepared and paired up to form ZnS-passivated CdS, (CdS)ZnS, and CdS-modified ZnS, (ZnS)CdS, particle films in a one-step process. For comparison purposes, sequential layer growth of CdS/ZnS and ZnS/CdS particle films was also conducted, and single compound particle films were prepared. These films were characterized with absorption spectrometry, photoluminescence spectroscopy, scanning electron microscopy, and powder X-ray diffraction spectra. The photoluminescence efficiency of the resulting composite particle film of ZnS-passivated CdS was significantly enhanced as compared to that of the plain CdS film, due to the effective passivation of surface electronic states of CdS by ZnS, a material with a higher conduction band than that of CdS. As for particle films of CdS-modified ZnS, a decay in photoluminescence efficiency was observed. The enhancement or decay in photoluminescence efficiency was much more pronounced for the passivated and modified system than for the sequential layer system, proportional to the interfacial area between the CdS and ZnS phases.

Cadmium Compounds↗

Zinc and the heat-labile enterotoxin of Escherichia coli.

Enterotoxigenic Escherichia coli is a major cause of diarrhoea in man. When zinc in concentrations of 10(-6) M or 10(-5) M was added to the growth medium, there was a significant increase in heat-labile enterotoxin production by each of six toxigenic strains. Zinc in these concentrations did not alter bacterial growth or the activity of preformed toxin. Other heavy metals did not enhance toxin production and o-phenanthroline, a relatively specific zinc-chelating compound, blocked the enhancing effect. The significance of these findings is discussed in relation to the use of supplemental dietary zinc.

Bacterial Toxins↗

Synthesis of SiO2-coated ZnMnFe2O4 nanospheres with improved magnetic properties.

A core-shell structured composite, SiO2 coated ZnMnFe2O4 spinel ferrite nanoparticles (average diameter of approximately 80 nm), was prepared by hydrolysis of tetraethyl orthosilicate (TEOS) in the presence of ZnMnFe2O4 nanoparticles (average diameter of approximately 10 nm) synthesized by a hydrothermal method. The obtained samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and field emission scanning electron microscopy (FESEM). The magnetic measurements were carried out on a vibrating sample magnetometer (VSM), and the measurement results indicate that the core-shell samples possess better magnetic properties at room temperature, compared with paramagnetic colloids with a magnetic core by a coprecipitation method. These core-shell nanospherical particles with self-assembly under additional magnetic fields could have potential application in biomedical systems.

Coated Materials, Biocompatible↗