Oxidation of low-density lipoproteins by OH. and OH./O2-. free radicals produced by gamma radiolysis.

The aim of this study was to analyze quantitatively the oxidative modification of low-density lipoproteins (LDLs) induced by OH. free radicals produced by gamma radiolysis, in the absence or in the presence of oxygen (action of OH. free radicals, or simultaneous action of OH. and O2-. free radicals, respectively). The effects of increasing radiation doses on aqueous LDL solutions have been monitored by several parameters: a decrease in endogenous vitamin E, the formation of thiobarbituric acid-reactive substances (TBARS) and conjugated dienes, the appearance of a differential fluorescence (excitation wavelength = 360 nm), and an increase in the relative electrophoretic mobility. Initial radiation yields (decrease in vitamin E, formation of TBARS) have been determined at pH 7 as a function of LDL concentration (from 0.75 to 9 g liter-1). From the comparison of these yields with those of OH. and O2-. free radicals produced by water radiolysis, we have deduced reaction mechanisms for the initiation of oxidation of LDLs by OH. and OH./O2-. free radicals.

Reactions of water radiolysis intermediates with pyrimidine and purine bases in aqueous BeF2 glasses: an EPR study.

Free radical formation by reaction of water radiolysis intermediates produced by X-irradiation in aqueous glasses containing 7 M BeF2 at 77 K with pyrimidine and purine constituents of DNA (10 mM) was studied by electron paramagnetic resonance (EPR) spectroscopy. Reactions of electrons and .OH radicals were observed; H. form a minority and their contribution was difficult to establish. The electrons form substrate radicals at 77 K, while .OH radicals, stabilized in the matrix at 77 K, become mobile at about 140K and in part react with solute molecules. The radicals formed by both reactions were characterized after isolation of the corresponding components by thermal annealing up to about 190 K and spectra simulation using literature parameters whenever possible. The spectra from cytosine gave strong evidence for heteroatom protonation following electron addition while those from adenine were somewhat less clear. The spectra of uracil and all methylated pyrimidines gave no evidence for the protonation state of the electron adduct. For the .OH radical, the reaction with uracil and cytosine was found to be addition to the 5,6-double bond, in line with studies using aqueous solutions. For all methylated pyrimidines, however, H-abstraction from the methyl group was dominant. .OH addition to adenine was found to take place at C2.

Concerning plasmon excitation in liquid water.

The existence of plasmon excitation produced by the interaction of fast charged particles in liquid water is examined critically from the theoretical point of view. By the analysis of the Fano index at different excitation energies and by comparing the real and imaginary parts of the dielectric function for both the liquid and the gas at unit density, we find no convincing evidence for plasmon excitation in the condensed phase of water. A density and a condensation effect on the dielectric function are observed. Implications of this finding for diffusion kinetics are discussed briefly. A procedure for the determination of the real and imaginary parts of the dielectric function from the dipole oscillator strength distribution is presented.

Remediation of groundwater polluted with chlorinated ethylenes by ozone-electron beam irradiation treatment.

OH radicals formed in water radiolysis may be effectively used for the oxidative decomposition of trichloroethylene and perchloroethylene contained as micropollutants in groundwater. Addition of ozone to the water before irradiation causes the reducing species of the water radiolysis to be converted into OH radicals. Moreover, this eliminates the dose rate effect observed with irradiation alone. By the ozone-electron beam treatment greater than 95% of the organic chlorine content are mineralized, only negligible amounts of organic chlorine containing by-products are formed. AMES test has shown no mutagenic activity at all.

Transient thermal and mechanical response of water subject to ionizing radiation.

The ultrafast transient (10(-14) to 10(-12)S) thermal and mechanical response of water subject to ionizing radiations of different linear energy transfers has been investigated in order to understand the initial events which lead to cell mutation and lethality. Based on computational fluid dynamics, the production of a "thermal spike" around the trajectory of a charged particle and subsequent diffusion of deposited heart are calculated for particles with linear energy transfer (LET) of 4, 40, and 400 keV/microns. A radiation damage region (that is, the so-called "thermal core") is identified, and the transient behavior of the thermal core is studied. The local and transient environment has a dimension of nanometers, a scale which is of critical interest in understanding mechanisms of radiation damage in cells. The radius of the thermal core, Dd, at temperatures (or internal energy density) of up to 1,000 K, is observed to increase with LET, L, as Dd (in nanometers) = C4.L (in keV/microns)0.6, where, for example, C4 = 0.50 for T = 800 degrees C.

Differential and integral W-values for ionization in gaseous water under electron and proton irradiation: consistency of inelastic collision cross sections.

Differential and integral W-values for ionization in gaseous water for electron and proton irradiation have been analyzed from the theoretical point of view for consistency between ionization and total inelastic collision cross sections. For low-energy electrons, which are ubiquitous for all primary radiations, the experimental or compiled cross sections from different sources are sometimes not consistent with one another. A practical, self-consistent procedure is outlined in such cases. The high-energy asymptotic W-values for differential and integral ionization are calculated to be 33.7 and 34.7 eV, respectively, for electron irradiation and 34.6 and 32.5 eV, respectively, for proton irradiation. The computed variations of the W-values with energy are generally in good agreement with experiment. Integral primary W-values due only to the interactions between the incident particle and the water vapor are calculated to be 43.5 and 45.0 eV for electrons and protons, respectively, in the high-energy asymptotic limit.

Molecular product formation in the electron radiolysis of water.

The time dependence of the formation of a molecular product in radiation chemistry is linked to the yield of the product formed in scavenging experiments by a Laplace transform relationship. Kinetic modeling with deterministic methods is used to show that such a relationship can be used to describe the molecular product (H2 and H2O2) formation following the fast-electron radiolysis of water and of aqueous solutions. Experimental yields are fitted using an appropriate empirical function, and the time dependence of the yields of the molecular products in the absence of a scavenger is derived using the Laplace relationship.

Radiation-induced DNA damage as a function of hydration. I. Release of unaltered bases.

The release of unaltered bases from irradiated DNA, hydrated between 2.5 and 32.7 mol of water per mole of nucleotide (gamma), was investigated using HPLC. The objective of this study was to elucidate the yield of the four DNA bases as a function of dose, extent of hydration, and the presence or absence of oxygen. The increase in the yield of radiation-induced free bases was linear with dose up to 90 kGy, except for the DNA with gamma = 2.5, for which the increase was linear only to 10 kGy. The yield of free bases as a function of gamma was not constant in either the absence or the presence of oxygen over the range of hydration examined. For DNA with gamma between 2.5 and 15, the yield of free bases was nearly constant under nitrogen, but decreased under oxygen. However, for DNA with gamma greater than 15, the yield increased rapidly under both nitrogen and oxygen. The yield of free bases was described by a model that depended on two factors: 1) a change in the DNA conformation from a mixture of the A and C conformers in vacuum-dried DNA to predominantly the B conformer in the fully hydrated DNA, and 2) the proximity of the water molecules to the DNA. Irradiation of the inner water molecules (gamma less than 15) was less efficient than irradiation of the outer water molecules (gamma greater than 15), by a factor of approximately 3.3, in forming DNA lesions that resulted in the release of an unaltered base. This factor is similar to the previously published relative efficiency of 2.8 with which hydroxyl radicals and base cations induce DNA strand breaks. Our irradiation results are consistent with the hypothesis that the G value for the first 12-15 water molecules of the DNA hydration layer is the same as the G value for the form of DNA to which it is bound (i.e., the pseudo-C or the B form). Thus we suggest that the release of bases originating from irradiation of the hydration water is obtained predominantly: (1) by charge transfer from the direct ionization of the first 12-15 water molecules of the primary hydration layer and (2) by the attack of hydroxyl radicals generated in the outer, more loosely bound water molecules.

An improved cryofixation method: cryoquenching of small tissue blocks during microwave irradiation.

The metal contact method of rapid freezing is greatly improved by irradiating the specimen with microwaves at 2.45 GHz for a short period of time (50 ms), while pushing the specimen onto the surface of the copper block cooled by liquid N2. The microwave irradiation, together with two technical improvements (a light-mass plunger and a recently developed beta-gel shock absorber) for preventing bounce, produces a good freezing zone for squid retina, with high reproducibility for each experimental trial, extending from the contact surface to a depth of about 15 microns, which is comparable to the depth obtained by the metal contact method using liquid He in the absence of microwave irradiation. A good freezing zone was also experimentally demonstrated in specimens of rat liver and heart muscle. Microwave irradiation does not have appreciable effects on the ultrastructure of squid retina. The mechanism underlying the improvement in the rapid freezing under the microwave irradiation is discussed.

Relative induction of cyclobutane dimers and cytosine photohydrates in DNA irradiated in vitro and in vivo with ultraviolet-C and ultraviolet-B light.

SV40 DNA was irradiated in vitro and in vivo with UV-C (240-280 nm) and UV-B (280-320 nm) light, and damaged sites sensitive to digestion with Escherichia coli endonuclease III (endo III) and bacteriophage T4 endonuclease V (endo V) were quantified. The frequency of endo III-sensitive sites (primarily cytosine photohydrates) induced was 1-2% of the frequency of endo V-sensitive sites (cyclobutane dimers) in both purified SV40 DNA and intracellular episomal SV40 DNA. Endo III- and endo V-sensitive sites in DNA were induced in the same relative proportion at both UV-C and UV-B wavelengths. We found no evidence to support earlier inferences that intracellular conditions enhance the formation of cytosine photohydrates or other monobasic forms of DNA damage.

Simulation of the passage of fast electrons and the early stage of water radiolysis by the Monte Carlo method.

A numerical computer simulation of the processes of the interaction of electrons with liquid water and vapor was performed, beginning with the absorption of the energy of ionizing radiation and including the chemical changes in the medium. The specific features of the liquid phase compared with the gaseous phase were taken into account. Among them are the decrease of the ionization potential and collective excitations of the plasmon type. The mass stopping powers and ranges of electrons in liquid water and vapor were calculated. Within the frames of the stochastic model the kinetics of water radiolysis in the picosecond range of radiolysis was calculated by the Monte Carlo method. The mechanism of water radiolysis was found with the electron-ion recombination and the reactions of quasi-free and solvated electrons taken into account.

Weiss lecture. Applications of the radiation chemistry of water: acid rain and nuclear power.

The radiation chemistry of water is sufficiently well known under ambient conditions that it is widely used to study the chemistry of free radicals in aqueous solution. One topical application described here is the hydroxyl radical-driven oxidation of sulphur dioxide to sulphuric acid in cloudwater to form acid rain. Another area of current interest is the effects of radiation on the cooling water of pressurized water reactors at ca. 300 degrees C. In studying these effects new information is also being gained on the fundamental processes in the radiation chemistry of water and on the kinetics of fast reactions.

Temperature response of biological materials to pulsed non-ablative CO2 laser irradiation.

This paper presents surface temperature responses of various tissue phantoms and in vitro and in vivo biological materials in air to non-ablative pulsed CO2 laser irradiation, measured with a thermocamera. We studied cooling off behavior of the materials after a laser pulse, to come to an understanding of heat accumulation and related thermal damage during (super) pulsed CO2 laser irradiation. The experiments show a very slow decay of temperatures in the longer time regime. This behavior is well predicted by a simple model for one-dimensional heat flow that considers the CO2 laser radiation as producing a heat flux on the material surface. The critical pulse repetition frequency for which temperature accumulation is sufficiently low is estimated at about 5 Hz. Although we have not investigated the ablative situation, our results suggest that very low pulse frequencies in microsurgical procedures may be recommended.

[Study of a population sample conducted using the bioenergy gold test]. / Indagine su un campione di popolazione condotto mediante il test all'oro della bioenergia.

Experiments carried out using the bioenergy gold test showed that a bioradiant subject working on water without touching, is able to modify the evolution of the gold colloid generated by chemical reaction in the treated water sample. To complete these researches, experiments were carried out on 50 pranotherapeutic practitioners and on 50 normal subjects. Statistical analysis shows that the results in normal subjects differ from those in the pranotherapeutic practitioners. These observations confirm that pranotherapeutists act physically on the water, modifying the structure of the liquid and the chemical gold test is able to reveal these changes.

The kinetics of radiation-induced strand breakage in polynucleotides in the presence of oxygen: a time-resolved light-scattering study.

The time-resolved light-scattering changes of aqueous, aerated solutions of poly-C, poly-U and poly-A at pH 7.8, following pulse irradiation, have been studied as indices of strand break formation. With doses of 4-24 Gy/pulse a number of kinetically distinct components have been detected. For the poly-pyrimidines an immediate and fast reduction (tau 1/2 less than or equal to 50 microseconds) in light-scattering intensity (LSI), accounting for approximately 20% of the total LSI change, is followed by a much slower loss (k1 approximately 1.6 s-1) which constitutes their major LSI change. For poly-A a similar fast component is observed, present to an extent equivalent to the one noted with poly-C; it constitutes, however, over 50% of the purine polynucleotide's total response, with the remainder of the change being a slower loss (tau 1/2 approximately 0.09 s). Optical pulse radiolysis studies of poly-C and poly-U, in support of the LSI investigations, show that transient absorbances in a region assigned to base peroxyl radicals decay in a complex fashion, with some at a rate equivalent to that for the slow (major) component of LSI loss. These observations support a proposal that the rate-limiting step of major strand breakage for these polynucleotides, in the presence of oxygen, is a base peroxyl radical-mediated abstraction of a H-atom from an adjacent sugar moiety (Bothe et al. 1986), with the resulting sugar peroxyl radicals then leading to strand break formation at a rate equivalent to that for loss of the initial, fast LSI components. These latter processes are attributed to strand breaks arising from the direct interaction of .OH with the polynucleotide sugar phosphate backbone.

Two-quantum UV photochemistry of nucleic acids: comparison with conventional low-intensity UV photochemistry and radiation chemistry.

The action of high-intensity laser u.v. radiation on nucleic acid molecules and their constituents in vitro and in vivo is compared with the results of low-intensity u.v. photolysis and gamma-radiolysis.

Direct simultaneous production of [15O]water and [13N]ammonia or [18F]fluoride ion by 26 MeV proton irradiation of a double chamber water target.

A simple double liquid chamber target was developed to provide the option for simultaneous production of [15O]H2O and either 13N or 18F using a single proton beam. Irradiation of natural water in a thin aluminium front chamber produced [15O]H2O by the 16O(p, pn)15O reaction directly. Large (0.5-1.0 Ci) doses of sterile [15O]H2O (greater than 99.95% radionuclide purity) were routinely prepared in 1 min from end of 20 microA bombardments using this target and an in-line mixed bed ion exchange column purification. Water in the thin front chamber degraded proton energies on exit to 20-18 MeV. The rear silver liquid chamber was threefold thick to 17 MeV protons in water and it efficiently produced either 13N by the 16O(p, alpha)13N reaction or [18F]fluoride ion by the 18O(p, n)18F reaction. Both target chambers were overpressurized with at least 6 atm of gas to minimize boiling/cavitation of water at high beam currents. Using hydrogen as the overpressure gas on the back chamber and an in-line anion exchange column radionuclidic cleanup process, high yields of sterile, aqueous [13N]NH3 (40-200 mCi; 20 microA) were produced directly from the back chamber at the same time that [15O]H2O was being produced from the front chamber. The combination of this target system with a cyclotron capable of generating 26-30 MeV protons provides great flexibility and simplicity for rapid, high volume production of the three best validated and most widely used radiopharmaceuticals at the present time in clinical positron emission tomography: [15O]H2O, [13N]NH3 and [18F]FDG.