Free radicals in irradiated wheat flour detected by electron spin resonance

By electron spin resonance (ESR) spectroscopy, we revealed free radicals in wheat flour before and after γ-ray inrradiation and their thermal behavior during heat treatment. The ESR spectrum of wheat flour before irradiation consists of a sextet centered atg=2.0 and a singlet signal at the sameg-value position. The first one is attributable to a signal with hyperfine (hf) interactions of Mn²⁺ ion (hf constant, 7.4 mT). The second signal originates from the carbon-centered radical. Upon γ-ray irradiation, however, a new signal with two triplet lines at the low- and high-field ends was detected on the Mn²⁺ sextet lines. We analyzed the triplet ESR lines as due to powder spectra (rhombicg-tensor symmetry) with nitrogen (¹⁴N) hf interactions. This indicates that a new organic radical was induced in the conjugated protein portion of wheat flour by γ-ray irradiation. The intensity of the organic free radical atg=2.0 detected in irradiated wheat flour increased monotonically under thermal treatment. The analysis of the time-dependent evolution process on the basis of the theory of transient phenomena as well as the nonlinear least-squares numerical method provided a unique time constant for the radical evolution in wheat flour during thermal treatment.     

ESR and TL studies of irradiated Anatolian laurel leaf (Laurus nobilis L.)

Laurel leaf (Laurus nobilis L.) samples that originated from Turkey were analyzed by electron spin resonance (ESR) and thermoluminescence (TL) techniques before and after γ-irradiation. Unirradiated (control) laurel leaf samples exhibit a weak ESR singlet centered at g=2.0020. Besides this central signal were two weak satellite signals situated about 3 mT left and right to it in radiation-induced spectra. The dose–response curve of the radiation-induced ESR signal at g=2.0187 (the left satellite signal) was found to be described well by a power function. Variation of the left satellite ESR signal intensity of irradiated samples at room temperature with time in a long term showed that cellulosic free radicals responsible for the ESR spectrum of laurel leaves were not stable but detectable even after 100 days. Annealing studies at four different temperatures were used to determine the kinetic behavior and activation energy of the radiation-induced cellulosic free radicals responsible from the left satellite signal (g=2.0187) in laurel leaves. TL measurements of the polymineral dust isolated from the laurel leaf samples allowed distinguishing between irradiated and unirradiated samples.     

ESR experiments with egg shells of chickens

The electron spin resonance spectra fromGallus domesticus egg shells exhibit a strong free radical singlet, a spectrum due to Mn²⁺ ions in a calcite site, a low field line line atg≈30/7 due to Mn²⁺ in a rhombic site, and spectral lines arising from Fe³⁺ ions. Details of the ESR spectral lines did not correlate with fertile, non-fertile or color type egg-shell characteristics.     

Electron Spin Resonance Spectroscopy of Gamma-Irradiated Glucose Polymers

Using electron spin resonance (ESR) spectroscopy, we revealed the irradiation-induced radicals in cellulose and starch. Before gamma-ray irradiation, no ESR signals were observed in both the glucose polymers. However, after gamma-ray irradiation, a singlet at g = 2.0 was observed, and a pair of side signals appeared simultaneously. The side signals were found at the symmetric field positions at both sides of the singlet signal. The side signals were visible in cellulose but not in starch. The side signals are found to be a precise indicator for irradiation effects in cellulose. They are originated from neither the peroxide radical of glucose polymer nor the so-called cellulosic radicals. By the simulation method, we found that the side signals are originated from a triplet due to a hyperfine interaction with two protons. By the theoretical simulation, we revealed that the signal undergo the rotational motions rather than rigid limit state (or no motion).     

ESR studies of sepiolites

The electron spin resonance (ESR) spectra for each beige and brown sepiolites from Polatli-Ankara, Turkey, a clay mineral of Mg₈Si₁₂O₃₀(OH)₄(OH₂)₄(H₂O)₈, at 77 K have their own single characteristic peak atg ≈ 1.99, which begins to anneal from 437 and 536°C, respectively. The sextet lines of Mn²⁺ were also observed in addition to two peaks (g = 4.4 and 5.0) associated with Fe³⁺. A high-quality sepiolite called “meerschaum” from Sepetci-Eskisehir, Turkey, has two characteristic peaks atg ≈ 1.99, which begins to anneal from 419°C, and atg ≈ 2.03. ESR intensities of the signal atg ≈ 1.99 for beige, brown sepiolites and meerschaum are enhanced by γ-ray irradiation to give equivalent dosesD _E = 11.8 ± 3.4, 4.7 ± 2.3 and 4.6 ± 1.2 kGy, respectively. The ESR ages obtained by assessing the annual dose rate from the content of²³⁸U,²³²Th and⁴⁰K determined by γ-ray spectroscopy are 1.8 ± 0.8, 0.7 ± 0.5 and 0.9 ± 0.2 Ma, respectively, falling into the Pliocene Epoch in geological time scale in agreement with the stratigraphy.     

Simulation analysis of ESR spectrum of polymer alkyl-C60 radicals formed by photoinitiated reactions of low-density polyethylene

Polymer alkyl-fullerene (P-C₆₀) radical adducts produced by ultraviolet (UV) photoinitiated reactions between low-density polyethylene (LDPE) and C₆₀ in the presence of benzophenone (BP) as a photoinitiator have been detected and identified for the first time by electron spin resonance (ESR) and confirmed by simulation analysis of the spectrum. A well-resolved ESR spectrum was recorded in situ upon UV irradiation of the LDPE/BP/C₆₀ sample in the molten state (413 K). Detailed analysis of hyperfine structures shows that the observed spectrum is composed of three components: a broad singlet atg = 2.0025 from the C₆₀ radical anion; an innermost pair of¹³C satellites; and a 12-line spectrum superposed on the broad singlet. The simulation analysis of the spectrum shows that the 12-line spectrum is due to the overlapping of two kinds of radical adducts of tertiary carbon-C₆₀ (A) and secondary carbon-C₆₀ (B), which have slightly differentg-values and almost the same integral intensity I_A/I_B (48.4/51.6). The spectrum simulated on the basis of the¹H and¹³C hyperfine interaction parameters is in good agreement with the observed spectrum. These results provide positive evidence that the C₆₀-bound LDPE materials can be obtained directly by a simple method of BP-photoinitiated reaction of the LDPE/C₆₀ system.     

Radical formation in lithium trifluoromethane-sulfonate for ESR dosimetry

Lithium trifluoromethane-sulfonate (Li-TFMS:CF₃SO₃Li) irradiated by γ-rays showed an electron spin resonance (ESR) powder spectrum having the rhombicg-factor ofg _xx = 2.0259 ± 0.0005,g _yy = 2.0112 ± 0.0005 andg _zz = 2.0025 ± 0.0005 and a triplet hyperfine coupling constant ofA _xx/gβ= 0.8 ± 0.15 mT.A _yy andA _zz are not obtained because of the broadened spectrum. The energy levels,g-factor,A _xx/gβ and optical absorption spectrum of several conceivable radicals such as C^⋅F₂SO₃Li, CF₃-S-O^⋅ and CF₃-S-O-O^⋅ have been calculated by softwares MOPAC-V2 and Gaussian-98 based on ROHF (Restricted Hatree-Fock for open shell molecule). The most probable radical was ascribed to CF₃-SO^⋅ from both calculated and experimental results. The response to γ-ray dose and the thermal stability have been studied in addition to the effect of UV illumination for possible use of the signal intensity in ESR dosimetry. The obtained number of free radicals per 100 eV (G-value) was 1.23 ± 0.40.     

ESR studies on calcite encrustation on Fili neotectonic fault, Greece

Electron spin resonance (ESR) study was done on calcite encrustation on Fili neotectonic fault surface, Greece. Normally such calcite encrustations on fault surfaces are not observed. Significantly, the ESR study has detected the presence of nitrate NO₃²⁻ radical in this calcite encrustation, havingg _⊥=2.0063±0.0001 and hyperfine coupling constantA _⊥=3.44 mT, the second such detection of nitrate NO₃²⁻ radical following a sample from Scott Glacier, Antarctica. From isochronal thermal annealing measurement the NO₃²⁻ radical was found to be quite stable, only fully annealed at 475°C. This study also shows that the ESR, as a tool, can be suitably applied to date the age of formation of the calcite encrustation with SO₃⁻ as an ESR dating signal by additive γ-ray irradiation. A preliminary estimation indicates the age of formation of calcite precipitation at Fili fault, Greece to be about 5600 years.     

Relaxation Behaviors of Free Radicals From γ-Irradiated Black Pepper Using Pulsed EPR Spectroscopy

Using electron paramagnetic resonance (EPR) spectroscopy, we revealed the relaxation behaviors of free radicals in γ-irradiated black pepper. Upon γ-irradiation, typical doublet peaks were detected. Relaxation times (T ₁ and T ₂) were observed using pulsed EPR. We found that T ₁ and T ₂ values varied with the γ-irradiation dose levels and these values showed a dependence on the dose level of the γ-irradiation treatment.     

Effect of irradiation on ethyl 2‐amino‐4,5,6,7‐tetrahydrobenzo[b]thiophene‐3‐carboxylate: an ESR study

Ethyl 2‐amino‐4,5,6,7‐tetrahydrobenzo[b]thiophene‐3‐carboxylate [C₁₁H₁₅NO₂S] was synthesized by the Gewald method. Its single crystals were grown from an alcohol/ethyl acetate solution at 15 °C and characterized using IR and ¹H‐NMR. These single crystals were irradiated for 72 h at 298 K by a ⁶⁰Co gamma source with a dose speed of 0.864 kGy/h. After irradiation, electron spin resonance (ESR) measurements were carried out to study radiation‐induced radicals in the temperature range from 120 to 450 K. Additionally, for the single crystal, ESR angular dependencies were measured in the xy, xz and yz planes of the substance. This irradiated single crystal was analyzed based on the ESR spectra. Analysis of the spectra revealed that the radical was formed by a C–H bond fission at the carbon end of the substance. It was also observed that the color of the sample changed after irradiation. The hyperfine and g parameters were determined from the experimental spectra. It was inferred from these results that the hyperfine parameters and g value exhibited anisotropic behavior. The average values of these parameters were calculated as follows: g = 2.0088, A_H1=H2 = 20.70 G, A_H3=H4 = 10.80 G, A_Ha = 4.59 G, A_Hb = 3.24 G and, A_N = 6.10 G. Copyright © 2011 John Wiley & Sons, Ltd.     

Identification of free radicals in irradiated MA-AMPS copolymer

Methacrylamide-2-acrylamido-2-methylpropanesulphonic acid (MA-AMPS) (80:20) is subjected to n -irradiation and the generated free radicals are identified by the electron spin resonance (ESR) technique. The ESR spectrum "obser"ved for MA-AMPS (80:20) has shown a complex line shape, indicating the presence of more than one free radical. Computer simulations are employed to unravel the radicals responsible for the ESR spectrum. Radical "identification has been done with the magnetic parameters employed during computer simulation. The observed ESR spectrum of the copolymer is simulated to be a superposition of component quartet, quintet and singlet spectra. The component spectra are assigned to ～CH 2 - . (CONH 2 )-CH 2 ～ or ～CH 2 - . H-CH 2 ～, . H 3 radicals, "respectively. The possibility of formation of such radicals in the sample material has been discussed.     

ESR dosimetric properties of talc and zircon

Two silicate minerals talc (Mg₃Si₄O₁₀(OH)₂) and zircon (ZrSiO₄) with different crystal lattice structures were subjected to ESR dosimetric studies. Zircon shows anisotropic ESR signals at g_xx = 2.0168, g_yy = 2.0076 and g_zz = 2.0033, which have been identified as a hole-center associated with Y³⁺ substituted at Zr⁴⁺ sites. Other characteristic signals were observed and identified. The ESR signal at g = 2.0033 showed positive response to γ-irradiation at 110 Gy and is suitable for use in dosimetry and dating of natural zircons.Talc (a magnesium sheeted silicate) exhibits ESR derivative spectrum characterized by the presence of Fe³⁺ at g = 4.28 and the hf-sixtet Mn²⁺ signals. This is due to the possible substitution of Fe³⁺ and Mn²⁺ in the Mg²⁺ octahedral sites, respectively. The enhancement of the Mn²⁺ sixtet by γ-irradiation increases the area occupied by the signals that makes it difficult for use with dosimetric applications.     

The magnetic hyperfine field at Cu in Fe,Co and Ni and the magnetic moment of the 41 keV, 2+ state of62Cu

The magnetic hyperfine interaction of Cu in Fe, Co and Ni was studied by means of the γ-γ perturbed angular correlation method using⁶²Zn(⁶²Cu) as a probe. With the publishedg-factor (g=+0.661(12)) of the 41 keV, 2⁺ state hyperfine fields ofB _HF=16.95(51) T,B _HF=13.15(41) T andB _HF=4.05(30) T atT=0 K for Cu in Fe, Co and Ni are derived, respectively. The systematic discrepancy of these values with several independent measurements of these hyperfine fields is removed by deriving a new value ofg=0.55(5) for the 41 keV, 2⁺ state of⁶²Cu.     

Electron spin resonance in X-irradiated single crystal of strontium tartrate tetrahydrate

The electron spin resonance spectra of an irradiated single crystal of strontium tartrate tetrahydrate (SrC₄H₄O₆·4H₂O) grown from silica gel have been investigated. Two species of free radical were observed at room and liquid nitrogen temperatures. The free radicals were found to be the result of the splitting of a C-H bond of the tartrate ions contained in the unit cell. The unpaired electron of each radical specie interacts with two nonequivalent protons giving rise to hyperfine splittings of relatively small magnitude. The g factors of the radicals were found to be almost isotropic and have similar values and it was very difficult to determine the ESR parameters from experimental patterns directly. A least-squares method, proposed earlier, was used to analyze the observed experimental patterns at various orientations.The existence of two nonequivalent radicals is believed to be the result of the nonplanarity of the two halves of the tartrate ions. The H nuclei giving rise to the hyperfine splittings are the protons of the hydroxyl groups attached directly to the unsaturated carbon atoms and those attached directly to the other asymmetric carbon atoms (β protons). The principal elements of the hyperfine splittings for the observed radicals were: Radical I: ?9.02, ? 2.84, ?0.47 and ?1.66, ?1.54, ?0.89. Radical II: ?10.16, ?7.83, ? 1.51 and 0.00, ?1.58, ?1.06. The radicals were found to be very stable, the ESR patterns being undiminished for more than six months after the irradiation.     

An electron spin resonance study of radical decay in γ-ray irradiated pepper by thermal treatments

Applied Magnetic Resonance - We examined by electron spin resonance (ESR) spectroscopy the thermal decay of radicals as induced by γ-irradiation on pepper. Upon irradiation, the satellite...     

Electron spin resonance in amorphous Si and Ge doped with Mn

ESR signal with hyperfine structure due to Mn and that due to dangling bonds are observed. From the magnitude of the hyperfine structure constant, Mn is considered to locate within voids without making a covalent bond with the host atom in the form of Mn²⁺. The intensity of the ESR signal due to dangling bonds decreases with the increase of that due to Mn, so it is likely that electrons are transfered from Mn to dangling bonds and their unpaired electrons are paired up.     

Electron paramagnetic resonance study of free radicals inγ-irradiated single crystal of tris(glycine) calcium(II) dibromide

Tris(glycine) calcium(II) dibromide single crystal has been irradiated with aγ-source to produce free radicals and the irradiated sample has been subjected toepr studies. The observed spectra reveal that an NH₄ radical is formed by rupturing glycine molecule due to irradiation. The unpaired electron is localized on the C-N bond. The proton hyperfine interaction on the unpaired spin shows orthorhombic symmetry and the spectroscopic splitting factor remains isotropic.     

Electron spin resonance studies on γ-irradiated KMnO4

Electron spin resonance (ESR) studies have been carried out on the radicals produced by the γ-irradiation of single crystals of KMnO₄.Analysis of the data yields at least two paramagnetic species. The first radical is produced by room temperature irradiation and gives a single line for each of two inequivalent magnetic sites. There is no resolvable hyperfine structure and the g tensor for the species is given by, g_b = g_μ′ = 2·0176, g_x′ = 2·0020, g_z′ = 2·0112. The spectrum is tentatively assigned to the O₃^? radical although MnO₂ and MnO₄ are also possibilities.The second radical is produced by irradiation at 77°K and the spectrum disappears irreversibly at slightly higher temperatures. Analysis of the very complicated spectra yields, g_b = 1·9617, g_x = 1·9452, g_u = 1·9940, A_b = 386 MHz, A₂ = 87 MHz, A₃ = 20 MHz. This spectrum is assigned to the MnO₄^?2 radical. The relationship of the radicals observed to the effect of high energy radiation on the decomposition of KMnO₄ in the light of current solid state theory is discussed.     

EPR characterization of organic free radicals in marine diesel

The intensive unresolved central line associated with organic free radicals in electron paramagnetic resonance (EPR) spectra of petroleum is interpreted as resulting from the superposition of signals from different radical species with very close g values. The mobility of a free radical in crude oil is relatively low due to the high oil viscosity. Aimed at characterizing free radicals in the oil byproduct, the present study is concerned with the investigation of marine diesel (bunker), a low-viscosity oil. Marine diesel was studied by EPR spectroscopy at X-band (9 GHz) in the temperature range from 170 to 400 K. Despite the viscosity at room temperature (2.5·10⁻³ kg/m·s) and the tumbling correlation time for free radicals of about 10⁻⁷ s suggesting a high mobility of free radicals in marine diesel, the EPR spectra at room temperature did not exhibit resolved lines, but only an envelope with a poor signal-to-noise ratio. The same behavior was observed from 170 to 373 K. Above 373 K, the EPR spectrum exhibited resolved lines: a superposition of a septet-quartet, a sextet-quartet and a quintet-quartet group of lines was identified with the following parameters: g = 2.003 ± 0.001, proton hyperfine couplings A = 6.41 ± 0.03 G (septet) and A′ = 1.82 ± 0.02 G (quartet); g = 2.003 ± 0.001, A = 6.21 ± 0.03 G (sextet) and A′ = 1.64 ± 0.02 G (quartet); g = 2.003 ± 0.001, A = 6.16 ± 0.03 G (quintet) and A′ = 1.83 ± 0.02 G (quartet), which were attributed to phenalenyl radicals and their derivatives. Below 373 K, phenalenyl dimerization prevented its detection by EPR.     

Characterization of free radicals generated from the reaction of Fe3+/Fe2+ withtert-butyl hydroperoxide and the effect of lanthanide ions

The inhibitory effects of lanthanide ions on the generation of free radicals from the reaction of Fe³⁺ and Fe²⁺ withtert-butyl hydroperoxide (^tBuOOH) were investigated by electron spin resonance (ESR) utilizing 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) as a spin trap. Peroxyl, alkoxyl, and carbon-centered free radicals generated from Fe³⁺-^tBuOOH system were successfully trapped by DMPO, whereas peroxyl radicals were not trapped in Fe²⁺-^tBuOOH system. Peroxyl and alkoxyl radicals are initial radical species generated from Fe³⁺ and Fe²⁺ systems, respectively. The carbon-centered radicals (^⋅CH₃) might be attributed to β-scission reaction of these alkoxyl radicals. The ESR signals of DMPO adducts of these radicals were quenched in the presence of lanthanides (Ln³⁺ or [Ln(cit)₂]³⁻), in concentration-dependent fashion. Moreover, the quenching effect of Ln³⁺ is closely related to the time the Ln³⁺ was added into the free-radical-triggered systems. The results reveal that there might be various mechanisms responsible for inhibiting generation and transformation of the free radicals. If Ln³⁺ and iron react with peroxide simultaneously, the complex formation of Ln³⁺ with^tBuOOH will be the main mechanism of the competitive inhibitory effect of Ln³⁺. Whereas if Ln³⁺ is added after iron, the inhibitory effect on the ESR signal of DMPO adducts might be interpreted preferentially by the coordination and magnetic dipole-dipole interaction between Ln³⁺ and DMPO adducts.