HYSCORE and Davies ENDOR study of irradiated ultra high molecular weight polyethylene

Ultra high molecular weight polyethylene (UHMWPE) has been studied with different magnetic resonance techniques to elicit information on the nature and the location of radicals generated during high energy irradiation. Field swept electron paramagnetic resonance, pulsed Davies electron nuclear double resonance and hyperfine sublevel correlation spectroscopic measurements allowed extracting for the first time the full ¹H hyperfine coupling tensors of the most abundant radical, i.e. a secondary alkyl radical and to ascertain the formation of allyl radicals in the first stages of the irradiation process. The ¹H hyperfine coupling tensors are analogous to those reported for single crystal irradiated polyethylene, suggesting that radicals generated in UHMWPE are located in the crystalline region of the polymer. Copyright © 2012 John Wiley & Sons, Ltd.     

Electron beam radiation effects on UHMWPE: an EPR study

Electron paramagnetic resonance (EPR) technique has been employed to detect and characterise a series of different radical species generated in ultra‐high molecular weight polyethylene (UHMWPE) via electron beam irradiation. Three different radical species have been found and assigned on the basis of their EPR spectra and of the related computer simulations. A secondary alkyl species, the prevalent one, is present immediately after irradiation, an allyl species appears only 24 h after irradiation when the alkyl species disappears.The third species, clearly visible at high microwave power only, has been observed for the first time and assigned to a tertiary alkyl carbon radical, whose formation is strictly connected with a Y‐shape crosslink and a migration of the unpaired electron on a carbon atom localised in an adjacent position. Copyright © 2011 John Wiley & Sons, Ltd.     

Radical protection by sunscreens in the infrared spectral range

One essential reason for skin ageing is the formation of free radicals by excessive or unprotected sun exposure. Recently, free radical generation in skin has been shown to appear not only after irradiation in the UV wavelength range but also in the infrared (IR) spectral range. Sunscreens are known to protect against radicals generated by UV radiation; however, no data exist for those generated by IR radiation. This paper has investigated four different, commercially available sunscreens and one COLIPA standard with regard to radical formation in the skin after IR irradiation, using electron paramagnetic resonance spectroscopy. The use of sunscreens has led to reduced amounts of radicals compared to untreated skin. Furthermore, absorption and scattering properties and the radical protection factor of the formulations were determined to investigate their influence on the radical protection of the skin. None of these formulations contained an optical absorber in the IR range. The protection efficiency of the sunscreens was shown as being induced by the high scattering properties of the sunscreens, as well as the antioxidants contained in the formulations.     

Sucrose radical-production cross-section regarding heavy-ion irradiation

We investigated the sucrose radical-production cross-section induced by heavy-ion irradiation. L-alanine was also used in order to compare radical yield and cross-section. The stable free radicals after irradiation were analyzed by electron paramagnetic resonance (EPR). The radical yield obtained by the irradiated samples had a logarithmic correlation with the LET (linear energy transfer). Quantitative EPR analyses showed that radical productions for sucrose and L-alanine vary both by different particle irradiation and the LET under the same absorbed dose. Furthermore, the cross-sections of radical productions for samples were calculated. Both cross-sections for C ions irradiation under LET 30 keV/microm at 50 Gy dose were approximately 3.0x10(-9) microm(2), taking account of the molecular areas of the samples. The values of the cross-sections imply that multiple ionizing particles involve producing stable radicals.     

Microstructural studies of electron beam-irradiated cellulose pulp

The effect of electron beam irradiation on the microstructure of cellulose has been investigated using positron annihilation lifetime spectroscopy (PALS) and electron paramagnetic resonance (EPR) Spectroscopy. PALS studies of irradiated cellulose samples showed that ortho-positronium (o-Ps) lifetime increases with an increase in dose up to 80 kGy and decreases at higher doses. The EPR signal of the irradiated cellulose matrix showed the presence of multiple radical sites. These results are discussed on the basis of chemical and physical changes occurring at the microscopic level in the cellulose due to irradiation.     

Radiolysis of confined water: hydrogen production at a high dose rate.

The production of molecular hydrogen in the radiolysis of dried or hydrated nanoporous controlled-pore glasses (CPG) has been carefully studied using 10 MeV electron irradiation at high dose rate. In all cases, the H2 yield increases when the pore size decreases. Moreover, the yields measured in dried materials are two orders of magnitude smaller than those obtained in hydrated glasses. This proves that the part of the H2 coming from the surface of the material is negligible in the hydrated case. Thus, the measured yields correspond to those of nanoconfined water. Moreover, these yields are not modified by the presence of potassium bromide, which is a hydroxyl radical scavenger. This experimental observation shows that the back reaction between H2 and HO* does not take place in such confined environments. These porous materials have been characterized before and after irradiation by means of Fourier-transform infrared (FT-IR) spectroscopy, electron paramagnetic resonance (EPR) and nuclear magnetic resonance (NMR) techniques, which helps to understand the elementary processes taking place in this type of environment, especially the protective effect of water on the surface in the case of hydrated glasses.     

Radical processes initiated by ionizing radiation in PEEK and their macroscopic consequences

Poly (ether ether ketone) was irradiated with gamma rays or electron beam to investigate the radical process. The generated paramagnetic species were observed by electron spin resonance spectroscopy at ambient temperature and in liquid nitrogen. The effect of microwave power on saturation of the particular spectra and thermal annealing effects were determined. The following radicals were identified: radical anion, phenoxyl radical, and phenylperoxy radical. Despite the fact that the intermediates were formed as a result of backbone cleavage causing degradation, the macroscopic features were almost unaffected by irradiation up to dose of 1500 kGy.     

Carbon dioxide activation by surface excess electrons: an EPR study of the CO2- radical ion adsorbed on the surface of MgO

The CO2- radical anion has been generated at the surface of MgO by direct electron transfer from surface trapped excess electrons and characterized by electron paramagnetic resonance spectroscopy. Both 13C and 17O hyperfine structures have been resolved for the first time, leading to a detailed mapping of the unpaired electron spin density distribution over the entire radical anion. The magnetic equivalence of the two O nuclei has been ascertained allowing a side-on adsorption structure at low-coordinate Mg2+ ions to be proposed for the surface stabilized radical.     

Comparative identification of irradiated herbs by the methods of electron paramagnetic resonance and thermoluminescence

Non irradiated and γ-irradiated dry herbs savoury (Savoury), wild thyme (Thymus serpollorium) and marjoram (Origanum) with absorbed dose of 8 kGy have been investigated by the methods of elecrtron paramagnetic resonance (EPR) and thermoluminescence (TL). Non-irradiated herbs exhibit only one weak siglet EPR signal whereas in irradiated samples its intensity increase and in addition two satelite lines are recorded. This triplet EPR spectrum is attributed to cellulose free radical generated by irradiation. It has been found that upon keeping the samples under the normal stock conditions the life-time of the cellulose free radical in the examined samples is ∼60–80 days. Thus the conclusion has been made that the presence of the EPR signal of cellulose free radical is unambiguous indication that the sample under study has been irradiated but its absence can not be considered as the opposite evidence. In the case when EPR signal was absent the method of TL has been used to give the final decision about the previous radiation treatment of the sample.     

A TRIR, TREPR and computational study on the reactivity and structure of the 2,2,2-trifluoroethoxycarbonyl radical

The 2,2,2-trifluoroethoxycarbonyl radical, 3b, has been generated by pulsed irradiation of 9-fluorenone oxime 2,2,2-trifluoroethyl oxalate 1b in carbon tetrachloride and acetonitrile solution. It was characterized by time-resolved electron paramagnetic resonance spectroscopy (EPR) and infrared spectroscopy. The radical has a lifetime in the range of microseconds and can be detected within the rise time of our time-resolved equipment before undergoing recombination or reactions with the solvent. No decarbonylation or decarboxylation was observed. In the presence of oxygen, the radical is quenched to yield the 2,2,2-trifluoroethoxycarbonylperoxy radical 4b, which has again a lifetime in the range of several microseconds. Time-resolved electron paramagnetic resonance spectroscopy (TREPR) allowed for the detection of a 1 : 1 : 1 triplet of the fluorene-9-iminyl radical 7 at g = 2.0032 and a 1 : 3 : 3 : 1 quartet with additional hyperfine splitting (HFS) due to proton coupling at g = 2.001 for the trifluoroethoxycarbonyl radical 3b. Calculations indicate that alkoxycarbonyl radicals can exist in conformations that are s-trans or s-cis with respect to the R-O-C(O) x dihedral. A comparison of experimental TREPR spectra with simulations indicates that the s-trans conformer is observed in the case of the ethoxycarbonyl radical, 3a. In the case of the trifluorethoxycarbonyl radical, 3b, however, the additional proton HFS observed shows that it is the s-cis conformer that is formed. As calculations give evidence for a fairly high activation enthalpy for s-cis-s-trans interconversion of alkoxycarbonyl radicals, this discrepancy is likely due to differing conformational preferences of the precursor molecules.     

The effect of temperature on the behavior of poly(o-chloroaniline) salts: conductivity and spectral studies

Conducting poly(o-chloroaniline) salis have been prepared by chemical polymerization of o-chloroaniline with five different acids. Composition and the extent of dopant in poly(o-chloroaniline) salt systems have been determined. Poly(o-chloroaniline) samples have been heat treated at four different temperatures 150, 200, 275 and 375°C and characterized by electron paramagnetic, infrared and electronic absorption spectral measurements. Thermal stabilities of the chemically synthesized poly(o-chloroaniline) salts have been studied by spectral methods. It was found that the polymer is apparently stable up to 200°C, and at around 275°C crosslinking takes place. It is inferred that the electron paramagnetic resonance signal observed in the conducting material does not arise from the current-carrying species, but rather from neutral paramagnetic species. No definite correlation exists between conductivity and the extent of dopant or spin concentration.     

EPR study of photoinduced charge transfer in a poly(3-hexylthiophene)-fullerene composite

Magnetic, relaxation, and dynamic parameters of radical pairs of positively charged polarons and negatively charged anion radicals of fullerene that are induced by photons with an energy of 1.7–3.4 eV are studied by the methods of photoinduced electron paramagnetic resonance for the poly(3-hexylthiophene)fullerene composite. The above charge carriers show mutual independence, which is provided by a different interaction with their microenvironment. The paramagnetic susceptibility of spin pairs reflects the dipoledipole interaction and activation dynamics of paramagnetic sites in the polymer-fullerene system. The rate of recombination of radical pairs is controlled by the mutual space distribution of carriers of various charges and by the energy of excitation photons. Quasi-one-dimensional diffusion of polarons along polymer chains and rotational diffusion of fullerene molecules about the selected molecular axis are likewise controlled by the energy of photons and can be described in terms of the activation Elliott hopping model. The dependence of the main values of magnetic, relaxation, and dynamic parameters of charge carriers on the energy of photons is explained by the inhomogeneous distribution of molecular clusters in the polymer-fullerene composite. The annealing of this composite leads to an enhanced formation of polymer crystallites and fullerene clusters. Hence, the effective dimension of the system increases and its electron characteristics are improved.     

Mechanophores with a Reversible Radical System and Freezing‐Induced Mechanochemistry in Polymer Solutions and Gels

Visualization and quantitative evaluation of covalent bond scission in polymeric materials are highly important for understanding failure, fatigue, and deterioration mechanisms and improving the lifetime, durability, toughness, and reliability of the materials. The diarylbibenzofuranone‐based mechanophore radical system enabled, through electron paramagnetic resonance spectroscopy, in situ quantitative evaluation of scission of the mechanophores and estimation of mechanical energy induced along polymer chains by external forces. The coagulation of polymer solutions by freezing probably generated force but did not cleave the mechanophores. On the other hand, cross‐linking led to efficient propagation of the force of more than 80 kJ mol^?1 to some mechanophores, resulting their cleavage and generation of colored stable radicals. This mechanoprobe concept has the potential to elucidate other debated issues in the polymer field as well.     

Analytical study on irradiated methylxanthine derivatives

The effect of ionising radiation on the physico-chemical properties of three derivatives of xanthine: caffeine, theophylline and theobromine, has been studied. The above-drugs in the solid phase have been irradiated with E-beam of the energy 9.96 MeV with the doses varied from 25 to 400 kGy. The effects of the irradiation have been examined by differential scanning calorimetry (DSC), electron paramagnetic resonance (EPR) and high-performance liquid chromatography (HPLC). The results have shown that the methylxanthine derivatives studied are resistant to ionising irradiation in the doses usually used for sterilisation (<50 kGy), which means that they are relatively radiochemically stable and can be sterilised by irradiation.     

Thioridazine induces immediate and delayed erythema in photopatch test

Thioridazine is a phenothiazine derivative that has been used as an antipsychotic; it rarely causes photosensitization. However, we noticed that this drug induced an erythematous reaction in a photopatch test. Six volunteers were patch tested with various concentrations of thioridazine and irradiated with a range of UVA doses, and the time courses of the color of and blood flow to the test sites were monitored. The free-radical metabolites of thioridazine generated under UVA irradiation and its effects on ascorbate radical formation were examined with an electron paramagnetic resonance (EPR) spectrometer in vitro. As a result, immediate erythema developed during UVA irradiation in most subjects when 1% thioridazine was applied for 48 h and irradiation doses were higher than 4 J cm(-2). Another peak of erythematous reaction was observed 8-12 h after irradiation. The in vitro examination detected an apparent EPR signal, which appeared when 2 mM thioridazine in air-saturated phosphate buffer was irradiated with UVA, whereas this reaction was attenuated under anaerobic conditions. The EPR signal of the ascorbate radical was augmented under both aerobic and anaerobic conditions. Thioridazine-derived oxidants and/or thioridazine radicals generated during UVA irradiation seem to play an important role in this unique phototoxic reaction.     

Conformational disorder in the propagating radical of dimethacrylate polymers

Photopolymerization of methacrylic monomers yields samples with trapped radicals that are easily detected by electron paramagnetic resonance (EPR) spectroscopy. Despite its simplicity, there is no general agreement about the interpretation of this spectrum, in particular, about the role of methylene β protons. An extensive ENDOR study of the propagating radical in photopolymerized dimethacrylates has been carried out in order to obtain detailed information about methylene hyperfine couplings and, thus, about radical conformation. It is shown that literature models are not able to reproduce the ENDOR results and that only accurate fitting of ENDOR spectra obtained by saturating the EPR spectrum at different positions gives reliable information about radical conformation, thanks to the exploitation of conformational selectivity. It turns out that most radicals are in the minimum energy conformation, but any possible conformation is assumed by non negligible fractions of radical.     

Energetic distribution of the electrons from a 200 keV beam in polyurethane layers : EGS4 calculation and FTIR analysis

The aim of this study is to characterize the chemical transformation of a polymer resulting from irradiation by a 200 keV electron beam. Thermoplastic PU polyetherurethane material was used and irradiation was performed with applied electron fluences in the range of 10¹⁴–10¹⁷ electron cm⁻² at 77 K.

The chemical changes have been observed by FTIR analysis of irradiated layers. A NH bond evolution study has allowed us to follow polymer degradation versus depth and fluence. The results have been compared to a simulation of electronic energy loss and to the energy spectrum of the generated electrons in the polymer using EGS4 code.     

Interaction of polypyromellitimide with nitrogen dioxide

The mechanism of interaction of nitrogen dioxide with aromatic polyimides is considered by the example of polypyromellitimide. The formation of stable radicals of acylarylaminoxyl, iminoxyl and phenoxyl types has been detected by electron paramagnetic resonance spectroscopy. Acylarylaminoxyl radicals were detected in polypyromellitimide after its exposure to nitrogen dioxide at room temperature followed by pumping nitrogen dioxide from the samples. Iminoxyl and phenoxyl radicals were formed during thermolysis of the nitration products of the polymer at 373 K. The proposed mechanism is based on the reaction of dimers of nitrogen dioxide in the form of nitrosyl nitrate. It was observed that intermediate radical cations and nitric oxide were formed in the primary reaction of electron transfer from the polyimide to nitrosyl nitrate. The subsequent cage reactions with participation of radical cations and nitric oxide give nitroso compounds and nitrates which are precursors of stable nitrogen-containing and phenoxyl radicals.     

Poly(ethylene glycol)/β-cyclodextrin covalent gel networks: host matrices for studying radical processes in plant extract–riboflavin systems following UV irradiation

Finding new, biocompatible matrices that allow us to model the generation of free radicals is of utmost importance for balancing the harmful and beneficial effects of the latter. In this respect, we report here the simultaneous encapsulation of the radical source and the antioxidant agent in a polyethylene glycol/β-cyclodextrin (PEG/β-CD) covalent gel network. We used electron paramagnetic resonance spectroscopy to evaluate the scavenging action of plant extracts (purple loosestrife, comfrey, milfoil, horsetail, thyme, carob, green coffee) embedded in PEG/β-CD gels. Free radicals were generated in situ by UV irradiation of riboflavin co-embedded in the gels. Prior to this, the extracts were characterized in what concerns their antioxidant activity, and their major polyphenolic constituents were quantified by liquid chromatography-electrospray ionization-tandem mass spectrometry. Purple loosestrife showed the highest antioxidant capacity, followed by comfrey and milfoil. Using the 5,5-dimethyl-1-pyrroline N-oxide spin trap, we have demonstrated that the gel-embedded extracts effectively scavenge the reactive carbon-centered free radicals generated in gel. The PEG/β-CD gels have been shown to be a valuable alternative matrix for the encapsulation of plant active principles having antioxidant activity. Moreover, co-encapsulation of the radical source transforms these gels into a controlled environment in which free radical processes can be tailored.     

Spectroscopic study of bituminous oxidative stress

Bitumen, as each organic substance, is a product which alters over time. Indeed, roads deteriorate under the effect of several phenomena. A number of studies have been undertaken to increase the quality of road's coating, mostly by adding polymer to bitumen. This work was based on the study, by electron paramagnetic resonance (EPR), FTIR and Synchronous UV fluorescence, of different base and modified bitumens after different treatments used to simulate the ageing (gamma irradiation, thermal treatment). Our purpose was to compare and correlate the results obtained by different techniques to improve the knowledge of bitumen's reactivity and evolution submitted to ageing phenomena.