Thiyl radicals in biosystems: inhibition of the prostaglandin metabolism by the cis-trans-isomerization of arachidonic acid double bonds.

This paper describes parallel and comparative experiments on the enzymatic cyclooxygenase (COX) driven conversion of arachidonic acid (AA, all-cis-5,8,11,14-eicosatetraenoic acid) into prostaglandins by using pure arachidonic acid and AA samples containing relatively small amounts of thiyl radical induced trans-isomers. The experiments were performed in a liquid aqueous model system using COX-1 as well as by the in vitro feeding of VD(3)-differentiated and LPS-stimulated promyelocytic HL-60 cells using the cell's own COX-2. In the model solution, all the different test methods used (oxygen consumption, ROS induced luminescence, and TMPD oxidation) indicated the greatly disproportionate, non-stoichiometric inhibition of the prostaglandin metabolism by the trans-isomers.

Efficiency and mechanism of the antioxidant action of trans-resveratrol and its analogues in the radical liposome oxidation.

trans-Resveratrol (trans-3,5,4'-trihydroxystilbene) is a nonflavonoid polyphenol reported to exert different biological activities, among them inhibition of the lipid peroxidation, scavenging of the free radicals, inhibition of the platelet aggregation, and anticancer activity as the most important. In order to enlighten the radical-scavenging mechanism of trans-resveratrol, stationary gamma-radiolytic experiments in liposomes and pulse radiolytic experiments in aqueous solutions were performed. Applying the stationary gamma-radiolysis together with the subsequent product analysis, reactions of lipid peroxyl radicals, LOO*, with trans-resveratrol and other natural antioxidants were investigated.

Transformation of phospholipid membranes by thiyl radicals via cis-trans isomerization of fatty acid residues.

Thiyl radical-mediated transformation of unsaturated fatty acid residues are reported. Beside the initiation of lipid peroxidation, thiyl radicals can efficiently cause isomerization of fatty acid residues in a catalytic manner. The latter process is observed in homogeneous solutions as well as in organized assemblies, leading to a denaturation of the natural all-cis-isomers of fatty acid residues of lipid bilayers.

Report on the third annual meeting of the Society for Biological Radiation Research, GBS '99.

During the past few decades radiation research has developed into specialized sub-disciplines, ranging from basic physics and chemistry to tumor biology and experimental radiotherapy. Scientific issues as well as the techniques and methodologies applied are subject to diverging discussion. The annual scientific meetings of the German "Gesellschaft für Biologische Strahlenforschung (GBS)" were established with the primary aim of allowing up-to-date transfer of current knowledge in any of the topics in radiation research and of promoting interaction between different research groups.

Electrochemical and NMR spectroscopic investigations of the influence of the probe molecule Eu(fod)3 on the permeability of lipid membranes to ions.

Investigating the action of the fluorinated europium complex Eu(fod)3 on lipid membranes we found that the complex facilitates the ion transfer through the membrane. Electric measurements on planar lipid membranes showed that the membrane conductivity increases considerably by insertion of the complex into the membrane. The increase in the conductivity was only obtained if both layers of the membrane were modified with the complex.

Mechanism of thiyl radical-catalyzed isomerization of unsaturated fatty acid residues in homogeneous solution and in liposomes.

NMR spectroscopy and gas chromatography were used on methanolic solutions of fatty acid methyl esters and on small bilayer liposomes to study the radical-induced denaturation of the fatty acid residues from the natural cis-configuration into trans-isomers. To analyze the mechanism of the thiyl radical-catalyzed lipid isomerization, we compared the effects of thiols on oleic and linoleic fatty acid residues using pulse radiolysis, gamma-radiolysis and chemolysis (AAPH) to generate thiyl radicals. The isomerization step takes place within the adduct of the thiyl radical to an olefinic group of unsaturated fatty acids, but not within the pentadienyl radical.

Differences in the reactivity of phthalic hydrazide and luminol with hydroxyl radicals.

The reactivity of 5-amino-2,3-dihydro-phthalazine-1,4-dione (luminol) and phthalic hydrazide with hydroxyl radicals was studied. HO*-radicals were generated by the Fenton reaction as well as by water radiolysis. Both luminol and phthalic hydrazide react with hydroxyl radicals under intense chemiluminescence (CL) emission.

Thiyl radical-induced cis/trans-isomerization of methyl linoleate in methanol and of linoleic acid residues in liposomes.

Purpose: To investigate the role of a thiol-containing biologically active compound in lipid peroxidation of membranes.

Materials And Methods: Thiyl radicals were generated from 3-(2-mercaptoethyl)quinazoline-2,4(1H,3H)-dione (MECH) using pulse radiolysis and gamma-radiolysis in aqueous and alcoholic solutions saturated with N2O. The products were analysed by 1H NMR and by HPLC.

Reactivity of cartilage and selected carbohydrates with hydroxyl radicals: an NMR study to detect degradation products.

It was investigated to what extent isolated, monomeric and polymeric carbohydrates as well as cartilage specimens are affected by hydroxyl radicals generated by gamma-irradiation or Fenton reaction and what products can be detected by means of NMR spectroscopy. Resonances of all protons in glucose and other monosaccharides as well as carbon resonances in 13C-enriched glucose were continuously diminished upon gamma-irradiation. Formate and malondialdehyde were found as NMR detectable products in irradiated glucose solutions under physiologically relevant (aerated) conditions.

Binding and relaxation behaviour of prodan and patman in phospholipid vesicles: a fluorescence and 1H NMR study.

The relative location, binding behaviour and the solvent relaxation behaviour of the polarity sensitive membrane probes 6-propionyl-2-(dimethylamino)naphthalene and 6-palmitoyl-2-[[trimethylammoniumethyl]methylamino]naphthalene chloride in vesicles composed of 1,2-dimyristoyl-sn-glycero-3-phosphatidylcholine or egg yolk lecithin have been compared using steady-state and time-resolved fluorescence as well as high resolution NMR measurements. The reconstructed time-resolved emission spectra show unambiguously that the observed spectral shifts in vesicle systems have to be assigned to time-dependent solvent relaxation processes rather than to a probe relocation mechanism. All fluorescence as well as the NMR relaxation data suggest a deeper localization of Patman in the membrane, sensing a less polar and/or more restricted probe environment.

Neurophysiological and neuropathological evaluation of primates exposed to ethylene oxide and propylene oxide.

Over 500,000 workers in the United States are exposed to ethylene oxide and propylene oxide. These two solvents are used as chemical intermediates, as well as components in the manufacture of fumigants and food preparation. The neurophysiologic and neuropathologic effects of these two organic oxides were investigated in five groups of 12 primates after exposure to 50 or 100 ppm ethylene oxide, 100 or 300 ppm propylene oxide, or no chemical (sham-exposed).

[NMR research on blood plasma for tumor detection--a method for mass screening?].

Recently, a simple NMR test was proposed to distinguish patients with and without malignant diseases by line-width analysis of methyl and methylene lipoprotein resonances in human plasma (4). We have reevaluated this proposed cancer detection technique at 250 MHz (magnet field strength 5.9T).

On the interaction of caffeine with nucleic acids. IV. Studies of the caffeine-DNA interaction by infrared and ultraviolet linear dichroism, proton and deuteron nuclear magnetic resonance.

The DNA-caffeine interaction at high concentration of caffeine (Cf) leads to an arrangement of Cf molecules outside of the DNA double helix with an orientation parallel to the bases both in the A and B form as demonstrated by infrared linear dichroism. Addition of DNA broadens the 1H NMR lines of Cf in aqueous solution indicating a specific binding. Intercalation is not the predominant mechanism, the deuterium relaxation time T1 = (38 +/- 7) ms and the estimated reorientation correlation time tau cb = 0.

Hydrophobic binding of phenoxyacetic and phenylacetic acids to horseradish peroxidase and human serum albumin: structure-activity relationships.

Studies of protein binding in homologous series of drugs are of great interest for drug research. Apparent binding constants of phenoxyacetic and phenylacetic acids to horseradish peroxidase and to human serum albumin are evaluated by NMR studies and an optical method. These constants are good parameters to describe hydrophobic interactions, and the results are in a good agreement with our protein binding model described previously.

Carrageenan in formula and infant baboon development.

Male and female infant baboons were reared from birth to 112 days of age on infant formulas containing concentrations of carrageenan varying from none to 5 times the concentration in commercially available formulas for human infants. Carrageenan content of the formula did not affect weight, characteristics of urine and feces, findinds on physical examination, hematological variables, blood chemical analyses, organ system weights, or the macroscopic and microscopic appearance of the gastrointestinal tract.