Dosimetric characteristics of different types of saccharides: An EPR and UV spectrometric study

The time stability and dose response of the free radicals produced in various types of “less-studied” mono- and disaccharides by γ-radiation is studied by EPR (Electron Paramagnetic Resonance) and UV spectrometry. The time evolution of the shape of the EPR spectra of irradiated saccharides is investigated from 5 min to 5 months after irradiation. The intensity of the stable EPR signal is studied as a function of the absorbed γ-dose in the range 0.5–20 kGy. Aqueous solutions of irradiated solid saccharides exhibit a UV absorption maximum in the range 250–290 nm. A linear dependency is found between the magnitude of the UV absorption maximum and the absorbed γ-dose. The time stability of the UV absorption maximum is also studied for every saccharide. The results are compared with those obtained for irradiated sucrose.     

ESR study of free radicals in mango

An electron spin resonance (ESR) spectroscopic study of radicals induced in irradiated fresh mangoes was performed. Mangoes in the fresh state were irradiated with γ-rays, lyophilized and then crushed into a powder. The ESR spectrum of the powder showed a strong main peak at g = 2.004 and a pair of peaks centered at the main peak. The main peak was detected from both flesh and skin specimens. This peak height gradually decreased during storage following irradiation. On the other hand, the side peaks showed a well-defined dose–response relationship even at 9 days post-irradiation. The side peaks therefore provide a useful means to define the irradiation of fresh mangoes.     

Intermolecular nuclear relaxation in paramagnetic solutions: from free radicals to rare earths

The principles of the intermolecular relaxation of a nuclear spin by its fluctuating magnetic dipolar interactions with the electronic spins of the paramagnetic surrounding species in solution are briefly recalled. It is shown that a very high dynamic nuclear polarization (DNP) of solvent protons is obtained by saturating allowed transitions of free radicals with a hyperfine structure, and that this effect can be used in efficient Earth field magnetometers. Recent work on trivalent lanthanide Ln³⁺ aqua complexes in heavy water solutions is discussed, including paramagnetic shift and relaxation rate measurements of the ¹H NMR lines of probe solutes. This allows a determination of the effective electronic magnetic moments of the various Ln³⁺ ions in these complexes, and an estimation of their longitudinal and transverse electronic relaxation times T_1e and T_2e. Particular attention is given to Gd(III) hydrated chelates which can serve as contrast agents in magnetic resonance imaging (MRI). The full experimental electronic paramagnetic resonance (EPR) spectra of these complexes can be interpreted within the Redfield relaxation theory. Monte-Carlo simulations are used to explore situations beyond the validity of the Redfield approximation. For each Gd(III) complex, the EPR study leads to an accurate prediction of T_1e, which can be also derived from an independent relaxation dispersion study of the protons of the probe solutes.     

Relative concentrations and relaxation properties of isomeric alkyl radicals in γ-irradiated n-alkane single crystals

The relative concentrations of alkyl radicals CH₃C?HCH₂R(I) and R'CH₂C?HCH₂R''(II) were measured at low microwave power in some n-alkane single crystals γ-irradiated at 77 K to a dose of 1 Mrad. The relative concentration of radical (II) increased as the number of carbon atoms became larger. The amount of radical (I) was in agreement with a mechanism where all CH bonds in an n-alkane molecule are raptured with the same probability followed by an isomerization of primary alkyl radicals to radical (I). In n-decane for instance this mechanism predicts 45.5% of radical (I) compared to the experimental value of 45.5%. Saturation measurements of radical (I) and radical (II) under slow passage condition showed that the spin-lattice relaxation time T₁ is shorter for radical (I) (ca. 3 × 10^?4s) than for radical (II) (ca. 80 × 10^?4s), while the spin-spin relaxation times T₂ are similar (ca. 2 × 10^?8s). The relatively short relaxation time T₁ in radical (I) is thought to originate from higher mobility of the end of the alkane chain, where the unpaired electron is localized, and also a modulation of the hyperfine coupling from protons in the nearby rotating methyl group. The broad linewidth in irradiated protiated cyrstals was by comparison with results from deuterated matrices concluded to depend on slightly distorted radicals in damaged regions (spurs, short tracks, blobs) and not on electron dipole-dipole interactions. Unresolved γ-proton couplings in radical (I) are thought to cause the spin-flip transitions at high microwave power.     

Spin relaxation and structure of light-induced spin-correlated PCBM−/P3HT+ radical pairs

The electron spin echo (ESE) technique is applied to determine the spin relaxation times of long-lived light-induced radicals and short-term spin-correlated radical pairs (SCRPs) formed by the laser flash of a composite consisting of [6,6]-phenyl-C₆₁-butyric acid methyl ether (PCBM) and poly-(3-hexylthiophene) (P3HT) at 80 K. The ESE signal dependences recorded to measure the longitudinal relaxation times of P3HT⁺/PCBM^? SCRPs and the free P3HT⁺ radical are fitted by the exp(-(t/T ₁)^0.6) dependence with T ₁ values lying in the microsecond time scale. The difference in the transverse spin relaxation times of the P3HT⁺/PCBM^? radical paira appeared after selective and non-selective echo-detected EPR spectrum excitation is explained by the instantaneous diffusion model. Based on the model, the magnetic interaction energy between the electron spins in P3HT⁺/PCBM^? SCRPs is estimated; E/? ～ 10⁶ s^?1.     

Irradiated bivalve mollusks: Use of EPR spectroscopy for identification and dosimetry

High energy radiation treatment of foodstuff for microbial control and shelf-life extension is being used in many countries. However, for consumer protection and information, the European Union has adopted the Directives 1999/2/EC and 1999/3/EC to harmonize the rules concerning the treatment and trade of irradiated foods in EU countries. Among the validated methods to detect irradiated foods the EU directives also include Electron Paramagnetic Resonance (EPR/ESR) spectroscopy.We describe herein the use of EPR for identification of four species of bivalve mollusks, i.e. brown Venus shells (Callista chione), clams (Tapes semidecussatus), mussels (Mytilus galloprovincialis) and oysters (Ostrea edulis) irradiated with ⁶⁰Co γ-rays. EPR could definitely identify irradiated seashells due to the presence of long-lived free radicals, primarily CO₂⁻, CO₃³⁻, SO₂⁻ and SO₃⁻ radical anions. The presence of other organic free radicals, believed to originate from conchiolin, a scleroprotein present in the shells, was also ascertained. The use of one of these radicals as a marker for irradiation of brown Venus shells and clams can be envisaged. We also propose a dosimetric protocol for the reconstruction of the administered dose in irradiated oysters.     

Micro-structure of gamma-ray irradiated polyethylenes studied by positron annihilation

Effects of gamma-ray irradiation on high density (HDPE) and low density (LDPE) polyethylenes were measured by positron annihilation at temperatures between 100 and 420 K. The effect of the irradiation on the intensity I₃ and the lifetime τ₃ of the longest lived component was significant below the glass transition temperature T_g, while they were little affected above T_g. For LDPE a marked minimum was observed in the I₃ vs T curve. The lower edge of the minimum, corresponding to glass II and glass I transitions, was found to shift to lower temperatures by the irradiation. In HDPE both I₃ and τ₃ decreased on irradiation mainly due to radiation induced free radicals. The gel fraction of HDPE was small when irradiated below T_m, while it rose sharply on irradiation near T_m. Positron lifetime parameters of this highly crosslinked HDPE showed a distinct difference compared to HDPE irradiated below T_m. Usefulness of the positron annihilation method is discussed in conjunction with studying micro-structure of polymers.     

Epr Spectroscopy of Adsorbed Spin-Labeled Peptides: Immobilization of Trichogin on the Titanium Oxide

The TOAC-spin-labeled peptide Trichogin GA IV adsorbed on the TiO₂ surface is studied. It is shown that the continuous wave (CW) electron paramagnetic resonance (EPR) spectrum does not depend on temperature in a wide range of 77–300 K. A pulsed EPR method of electron spin echo (ESE) utilizing a two-pulse sequence (π/2-τ-π) is used to study temperature dependence of the phase relaxation time, T_F. The T_F values are found to change from 750 ns to 100 ns in the interval of 77–300 K. The pulsed electronelectron double resonance (PELDOR) measurements utilizing the pulse sequence((π/2)_A,-T-π_B,-(τ-T)-π_A) show that the space distribution of spin labels on the surface remains uniform irrespective of the temperature, and provide the fractal dimension of the surface of 2.7±0.1. The obtained results testify that EPR pulse experiments can be used to study adsorbed spin-labeled molecules at room temperatures, i.e. not only at cryogenic temperatures.     

Electron paramagnetic resonance spectroscopy of γ-irradiated cellulose and related compounds

EPR studies were carried out on different irradiated cellulosic materials. The shape of the EPR spectrum was found to depend upon the fine structure of cellulose. The peak-to-peak distances of the large peaks on the differential curves were found to be 23.3 and 24.8 gauss, respectively, for the amorphous and recrystallized cellulose. The number of free radicals present per unit weight in the recrystallized cellulose and in the amorphous cellulose were found to be in the ratio of 2.1:1. The EPR spectrum of a sample of irradiated cotton crystallites which was soaked in acetone before being dried was markedly symmetrical, in contrast to the EPR spectra of samples of cotton linters and of cotton crystallites dried from water, and was considered to be a reflection of the lower intermolecular bonding in the former. For corresponding doses, the free radicals on cotton crystallites have the highest g value, followed by cotton linters, followed by regenerated cellulose I. The g value decreased as the irradiation dose was increased.     

Gamma irradiation effects on poly(hydroxybutyrate)

Brazilian poly(hydroxybutyrate), PHB, as well as its copolymer, poly(hydroxybutyrate-co-valerate), P(HB-co-HV), containing 6.3 mol% of valerate, were irradiated with γ radiation (⁶⁰Co) at ambient temperature and in the presence of oxygen. The viscosity-average molar mass (M_v) was analyzed by the viscosity technique using an Ostwald-type capillary viscometer. The polymers showed a decrease in molar mass with the increase in dose, reflecting the scissions that occurred at random in the main chain. The value G (scissions/100 eV of energy transferred to the system) and the parameter α (scissions per original molecule) were also obtained by the viscosity technique. The melting temperature (T_m) was determined by differential scanning calorimetry (DSC) and showed a decrease with increasing irradiation dose. Analyses of DSC also revealed double endothermic peaks, associated with the polymorphic transitions, which became a single peak with increased dose. Thermogravimetry analysis (TGA) revealed small differences between the decomposition temperatures of the irradiated and non-irradiated samples. The degree of crystallinity of PHB samples, on the other hand, which were obtained by the DSC and X-ray diffraction techniques, increased with the irradiation dose. Changes in the lattice parameter of the irradiated samples and in the size of the crystallites were also observed by X-ray diffraction. The samples used in this work did not pass through any purification process and were analyzed in powder form, exactly as they arrived from the factory.     

Effect of electron-irradiation on cross-link density and crystalline structure of low- and high-density polyethylene

Low- and high-density polyethylenes (LDPE and HDPE) were cross-linked in solid state by electron beam irradiation. Molar mass between cross-link joints, M_c, and cross-link density,ν, were calculated using rubber elasticity theory and hot set data. The results showed that the ν and creep modulus increased and creep strain and M_c decreased with increasing irradiation dose. As compared to HDPE, the LDPE had higher ν and lower M_c values at a similar irradiation dose. X-ray analysis and differential scanning calorimetry investigation of first heating cycle revealed no changes in crystalline structure of the irradiated samples. This was attributed to immobilization of radicals frozen in the crystalline phase. As a result of hindered mobility of the polymeric chains, these radicals were not able to cross-link the chains in the crystalline region. However, after melting of the crystals and during subsequent re-solidification process, different levels of crystallinity were developed depending on the applied irradiation dose. The irradiated samples with higher dose had lower crystallization and melting temperatures with reduced crystallinities. These confined crystallization behaviors, observed after a series of cooling and heating cycles, could be attributed to the decrease in the M_c values. The length of chain segment needed for usual crystallization by chain folding is decreased due to formation of cross-link joints and hence the crystallization process was hindered.     

EPR study of free radicals in non- and gamma-irradiated nutritive supplements containing anthocyanins concentrate from lyophilized red wine

Nutritive supplements Enoviton, Enoviton C and Enoviton CE containing standardized anthocyanins from lyophilized red wine, vitamins (some of them) and excipients were investigated by EPR spectrometry before and after gamma-irradiation. Non-irradiated samples exhibit one singlet line with g=2.0039±0.0002, most probably due to free radicals from anthocyanins. After irradiation with 10 kGy gamma-rays, tablets of Еnoviton, Еnoviton С and Еnoviton СЕ, all exhibit complex EPR signals centered at a g-value of g=2.0034. The EPR spectrum of irradiated Enoviton is different from that of Еnoviton С or Еnoviton СЕ due to the overlap of the spectra of microcrystalline cellulose and the background singlet spectrum present in all tablets with the EPR resonance due to irradiated ascorbic acid (in Еnoviton С and Еnoviton СЕ). Gamma-induced free radicals exhibit long time stability—for a six months period the intensity of central peak decrease with 30–40%.     

Degradation and stability of polyaniline on exposure to electron beam irradiation (structure-property relationship)

Polyaniline (PAni) was prepared by electrochemical polymerization and subjected to different doses of electron beam (EB) irradiation. The effect of EB irradiation causes both chain scission and cross-linking process in PAni, which depends on irradiation dose. The degree of chain scission and cross-linking in PAni by EB irradiation is characterized through XRD, TGA, DSC, solubility, EPR and electrical properties measurement. The results reveal that with increase in EB irradiation dose from 0 to 150 kGy DC and AC conductivity and dielectric constant are found to increase mainly due to the chain scission or further doping in PAni. Due to irradiation there is change in the structure of PAni, such as decrease in the d-spacing, inter-chain separation, thermal stability and T_g but increase in the percent crystallinity and solubility. With further increase in the EB irradiation dose from 150 kGy onwards the DC and AC conductivity and dielectric constant are decreased due to the cross-link formation or dedoping in PAni, which causes the decrease in percentage of crystallinity and solubility and increase in d-spacing, inter-chain separation, thermal stability and T_g of PAni.     

EPR evaluation of absorbed doses in γ-irradiated animal bone tissues

The accumulation of CO ₂ ^- radicals in γ-irradiated porcine, chicken, bovine, walleye pollack, and navaga bone tissues and chicken eggshells was studied by EPR spectroscopy for the purpose of detecting irradiated food and evaluating the dose absorbed during its radiation processing. It was found that, in the dose range 0–10 kGy, the concentration of radicals is a linear function of dose, and the variation coefficient of the radiationchemical yield of radicals is no higher than 30% for bone tissues from various biological species. The applicability of the additive dose method to the EPR dosimetry of irradiated beef was examined. A linear regression model used in the additive dose method was found to give overestimated results, as compared with an exponential fitting model.     

Evidence of dynamic heterogeneity as obtained from dielectric and brillouin light-scattering studies of poly(n-hexylmethacrylate)

We report dielectric relaxation and Rayleigh-Brillouin spectroscopic measurements on the side chain polymer poly(n-hexylmethacrylate), PHMA (T_g = 268 K), exhibiting a broad glass transition region. The dielectric loss curves can be represented by single Havriliak-Negami functions in the temperature range of 260–450 K. The width of the distribution relaxation function is a decreasing function of temperature up to T = 333 K ≊ 1.24 × T_g and remains virtually constant above that temperature. This is interpreted as marking the merging of the α-process with a slow β-relaxation in agreement with the value of the cooperativity length associated with the α-mode. Hence above that temperature, the relaxation times confirm well to an Arrhenius temperature dependence. The hypersonic dispersion deduced from the Brillouin spectra (210–550 K) surprisingly peaks at temperatures near T_g which bears no relation to the main α-relaxation. This structural relaxation is rather associated with the side hexyl group motion showing striking resemblance with the hypersonic dispersion in molecular liquids. It is conceivable that the observed damping in PHMA is dynamically related to the internal plasticization effect of the hexyl group. © 1996 John Wiley & Sons, Inc.     

Effect of gamma irradiation on linear low density polyethylene/magnesium hydroxide/sepiolite composite

Radiation crosslinking is generally used to improve the thermo-mechanical properties of the composites. A study has been carried out to investigate the effect of gamma radiation on the thermo-mechanical properties of linear low density polyethylene containing magnesium hydroxide (MH) and sepiolite (SP) as non-halogenated flame retardant additives. The developed composites are irradiated at different doses upto maximum of 150 kGy. Infrared spectra of the irradiated composites reveal the reduction in the intensity of O-H band with increase in the absorbed doses, thus indicates a distinct structural change in MH at higher doses. The thermogravimetric analysis results of unirradiated and composites irradiated at low doses (≤75 kGy) show two steps weight loss, which is changed to single step at higher doses with lower thermal stability. The melting temperature (T_m) and crystallization temperature (T_c) of irradiated composites are lowered with irradiation whereas Vicat softening temperature (VST) is increased. The increasing trend in gel content with increase in the absorbed dose confirms the presence of crosslinked network. The mechanical properties, results show significant improvement in the modulus of irradiated composites. The results also confirm that MH gradually loses its OH functionality with irradiation.     

Photoinduced formation of hydrogen peroxide in aqueous solutions of adenine derivatives at 77 K

The amount of hydrogen peroxide in aqueous solutions of adenine (A), adenosine (Ado), cytidine (Cyt), and thymine (T) containing 0.1 M NaCl and irradiated with near-UV light at 77 K is determined. It is established by comparing the results to data obtained earlier that the amount of H₂O₂ detected in the defrosted samples following identical irradiation falls in the order Ado > adenosine-5′-diphosphate (ADP) > A >> Cyt. The formation of H₂O₂ was not detected for T. The formation of H₂O₂ in solutions of adenine derivatives was observed when the samples were irradiated with light having wavelengths in the ranges λ = 240–400 nm and 290–450 nm. The latter covers only the long wave absorption range of these compounds. It is shown that the change in the intensity of irradiation that strongly affected the intensity оf EPR signals of irradiated samples prior to defrosting affected the amount of detected H₂O₂ only slightly, and the effect was not unidirectional. The results from determining H₂O₂ in the samples of adenine derivatives are compared to estimates of the content of free peroxyl radicals, obtained by analyzing EPR spectra. Plausible mechanisms of the processes are discussed.     

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.     

Electron spin relaxation times and rapid scan EPR imaging of pH‐sensitive amino‐substituted trityl radicals

Carboxy‐substituted trityl (triarylmethyl) radicals are valuable in vivo probes because of their stability, narrow lines, and sensitivity of their spectroscopic properties to oxygen. Amino‐substituted trityl radicals have the potential to monitor pH in vivo, and the suitability for this application depends on spectral properties. Electron spin relaxation times T₁ and T₂ were measured at X‐band for the protonated and deprotonated forms of two amino‐substituted triarylmethyl radicals. Comparison with relaxation times for carboxy‐substituted triarylmethyl radicals shows that T₁ exhibits little dependence on protonation or the nature of the substituent, which makes it useful for measuring O₂ concentration, independent of pH. Insensitivity of T₁ to changes in substituents is consistent with the assignment of the dominant contribution to spin lattice relaxation as a local mode that involves primarily atoms in the carbon and sulfur core. Values of T₂ vary substantially with pH and the nature of the aryl group substituent, reflecting a range of dynamic processes. The narrow spectral widths for the amino‐substituted triarylmethyl radicals facilitate spectral‐spatial rapid scan electron paramagnetic resonance imaging, which was demonstrated with a phantom. The dependence of hyperfine splittings patterns on pH is revealed in spectral slices through the image. Copyright © 2014 John Wiley & Sons, Ltd.     

Relation of the decay of free radicals in irradiated polyethylene to the molecular motion of the polymer and the configurations of the free radicals

Decay reactions of the free radicals produced in irradiated polyethylene (high-density and low-density materials) were examined in connection with the molecular motion of the matrix polymer. Three temperature regions, in which the free radicals decay very rapidly, at around 120, 200, and 250°K, were designated T_A, T_L, and T_B, respectively. The decay of the free radicals at these temperatures had activation energies in high-density polyethylene of 0.4 kcal/mole for T_A, 9.4 kcal/mole for T_L, and 18.4 kcal/mole for T_B. In low-density polyethylene these quantities were 0.7 kcal/mole for T_A, 23.1 kcal/mole for T_L, and 24.8 kcal/mole for T_B. Comparison of time constants for the decay reactions and for molecular motion of the matrix polymer indicate that the decay in T_A and T_B is closely related to molecular motion in the amorphous regions of the polymer. The decay of the free radicals at T_L in high-density polyethylene is due to molecular motion associated with local mode relaxation at lamellar surfaces, while that of low-density polyethylene is due to local mode relaxation in the completely amorphous region. Steric configurations of the free radicals which decay in the respective temperature regions were also investigated.