Evidence of polyphenols nitrosation by computer aided ESR spectroscopy

Polyphenols play an important role as model systems in transition metal derivatives for the preparation of macromolecular systems. Among the metal ions ironnitrosyl coordination chemistry has received much attention in the past because of its important role in inorganic and biological processes. In the case of Fe(I)(NO)₂ complexes with polyphenols ligands in solution, difficulties in the interpretation of the ESR spectra arise from complicated patterns due to simultaneous presence of different nitrogen nuclei directly bound to the metal ion or due to the presence of equilibria between species under slow exchange conditions. In order to overcome these difficulties the investigations reported here were carried out using computer simulation of ESR spectra combined with selective isotopic substitution of ¹⁴NO with ¹⁵NO. Resorcinol displays an unexpected nine lines ESR pattern at g=2.018 which can be explained only by considering more than two nitrogen atoms interacting with the unpaired electron delocalized over the metal complex.     

ESR spectroscopy of FeIII ions in sodium silicate glasses

The state of Fe^III ions doped in sodium silicate glasses of the composition (100 ? x)Na₂O-xSiO_2?y Fe₂O₃ (x = 75, 81 mol.%; y = 0.05?13 wt.%) was studied by electron spin resonance (ESR). X-band ESR spectra exhibited three resonance signals at g ≈ 2.0, 4.3, and 6. The computer simulation of ESR spectra was performed on the basis of spin-Hamiltonian of rhombic symmetry. The nature of observed signals was interpreted as a combination of five types of Fe^III complexes. Three of them were clustered iron ions and two other were isolated paramagnetic ones. The ratio of observed forms was found for different glass compositions and various total amounts of Fe^III ions in a matrix containing 0.55, 2.5, 4, 7, and 13 wt.% of Fe₂O₃.     

A local intercomparison study of ESR dosimetry using tooth enamel

Using electron spin resonance (ESR), tooth enamel is a possible dosimeter in case of a radiation accident. To check the present status of this technique, we conducted a local intercomparison study. We irradiated several samples of tooth enamel with a⁶⁰Co source. Three institutes in Belgium and The Netherlands recorded the ESR signal of the samples. The results of the measurements and the methods used are compared. It is concluded that ESR on tooth enamel can be a useful technique in accident dosimetry, provided further research is done.     

On optically detected ESR spectra from radical cations of liquid hydrocarbon solvents

The optically detected electron spin resonance (OD ESR) method has been employed to study the origin of radical-cation ESR signals in some saturated hydrocarbons with small amounts of 2.5-diphenyloxazol or p-terphenyl under radiolysis. In cyclohexane, the ESR, signal with resolved hyperfine structure was ascribed to c-C₆H₁₀⁺/PPO^? radical-ion pairs produced from primary c-C₆H₁₂⁺/PPO^? ones by monomolecular decay, of cyclohexane radical cations to cyclohexene radical cations. Cis- and trans-decalin under radiolysis accumulate 9,10-octalin which captures solvent holes and form 9,10-octalin radical cations giving a resolved OD ESR spectrum. 9,10-octalin is present in non-irradiated commercial decalin as an impurity. The OD ESR technique has been shown to be very sensitive to some impurities in hydrocarbon solvents.     

Time-resolved ESR study of the lowest excited triplet states of para-quinones in glassy matrices at 77 k

The lowest excited nπ* triplet of 9.10-anthraquinone, 1.4-naphthoquinone and 1,4-benzoquinone were studied in glassy matrices at 77 K using a time-resolved ESR method. The D value of the triplet state of 9,10-anthraquinone varied from ?0.351 cm^?1 in a polar solvent to ?0.318 cm^?1 in a non-polar solvent. Both 1,4-naphthoquinone and 1,4-benzoquinone in polar solvents showed triplet state spectra with a D value of ?0.330 cm^?1. A computer simulation revealed the existence of widely distributed zero-field splitting parameters in the glassy condition. These data are compared with an analysis of CIDEP results of para-quinones.     

ESR studies of non-silicate inorganic glasses through their glass transformation ranges

ESR spectra of three inorganic glasses doped with Mn²⁺ and Fe³⁺ have been studied through their glass transition temperatures (T_g). Spectral features in each case have been discussed with reference to site symmetries. The intensity of the ESR signal has been bound to decrease in the region of T_g. An attempt has been made to explain this interesting feature on the basis of a two-state model.     

Multifrequency ESR and ENDOR studies of ionomers

We describe methods for determining the local environment of cations and the process of ionic clustering in ionomers, using electron magnetic resonance spectroscopy. The distance between Cu²⁺ cations in perfluorinated membranes (Nafion) containing terminal sulfonic groups and swollen by water has been deduced from an analysis of ESR spectra at L (1.25 GHz), S (2.36 GHz) and X (9.36 GHz) bands, in membranes containing cupric ion concentrations in the range 1–30 percent of the total amount needed to fully neutralize the pendant acid groups. At higher cation concentrations ESR spectra indicate the presence of aggregated cations. The intercation distance determination is based on the simulation of spectra from isolated cations using distribution widths δg₁₁ and δA₁₁ and extraction of the residual width ΔH^R, which is due to dipolar interactions. No aggregation is detected in membranes swollen by less polar solvents such as methanol, dimethylformamide (DMF) and tetrahydrofuran (THF); these results are in contrast to SAXS experiments in membranes swollen by methanol, which exhibit the “ionic peak”. Cu²⁺-Cu²⁺ and Ti³⁺-Ti³⁺ dimers have been detected in Nafion swollen by water, methanol, DMF and THF, and have been characterized by an analysis of the spin-forbidden half-field Δm_s=2 transition, and by computer simulations. The intercation distance in the cupric dimers, deduced from the intensity ratio of the Δm_s=2 and Δm_s=1 dimer transitions, is 5.0±0.2 Å. A model for the dimer has been proposed, which explains the crosslinking of the polymer chains by the metal cations. ENDOR signals from ¹H, ²H and ¹⁹F nuclei have been detected in Nafion neutralized by Ti³⁺. The ENDOR results allow determination of the local environment of the paramagnetic cations, to a distance of ∼10 Å.     

ESR and electrical conduction in polypropiolamide

ESR and electrical conductivity measurements have been made on a recently prepared polymer, polypropiolamide. The polymer was obtained as a fine powder which exhibited a nearly Lorentzian line with a width between derivative maxima of 5.2 ± 0.1 gauss and a g value of 2.0036 ± 0.0005. The signal intensity increased with increasing molecular weight. The signal was retained in a dilute solution in formic acid with a slight narrowing of the line. Permanent changes were produced in the spectra at room temperature by heat treatments of the polymer at temperatures up to 800°K. The changes were similar for samples sealed in tubes containing air, dry nitrogen gas and a vacuum of 3 × 10^?5 mm of Hg. Spectra obtained at temperatures up to 500°K showed no dependence on the presence or absence of oxygen in the ambient atmosphere. The deresistance of pressed pellets of the polymer was measured in the temperature range 450°K to 525°K, and the results were described by the relation R = R₀c^E/kT. The activation energy E had a value of 1.2 ± 0.2 ev and the resistivity at 500°K was approximately 10¹³ ohm-em. The ESR signal is attributed to an intrinsic property of the polymer which is associated with a conjugated bond system along the polymer backbone. Neither the activation energy nor the magnitude of the resistivity suggest that the delocalized electrons associated with the conjugated bond system have produced unusual electrical characteristics in the polymer.     

ESR spectrometric characterization of the methyl viologen dosimeter in poly(vinyl alcohol) film

A dosimeter of poly(vinyl alcohol) (PVA) film containing methyl viologen dichloride (MV²⁺ (Cl^-)₂) was characterized by means of ESR and u.v. spectrometries. γ-irradiation of the MV²⁺-PVA dosimeter induced one-electron reduction of MV^2+· to thecation radical (MV⁺), thus giving rise to blue coloration. The resulting MV^+· showed an ESR signal with a g-factor of 2.0031. The yield of MV^+· at a given radiation dose was estimated from duplicate integral of the ESR first-derivative spectra by reference to 1,1'-diphenyl-2-picrylhydrazyl (DPPH). The yield of MV^+· thus estimated increased linearly with increasing the radiation dose up to about 1.4 Mrad. The ESR spectrometry of MV^+· showed a linear correlation with the u.v. spectrometric method reported previously.     

Optical and ESR studies of silver clusters

The optical and ESR spectra of Ag(O), Ag₂⁺ and Ag₄³⁺ centres formed in γ-irradiated aqueous and ethanol glasses have been monitored under identical conditions. The ESR spectra of the Ag(O) centres sugest that they initially retain the solvation of the parent Ag⁺ ions but that solvent molecules are gradually lost on annealing. This loss is reflected in marked high-frequency shifts in the electronic transitions. An intense band observed in the range 265–290 nm grew in simultaneously. This is assigned to Ag₂³⁺ ions. These have a well characterised ESR spectrum, but have not previously been studied optically.     

The effects of temperature on ESR spectrum of gamma-irradiated ammonium tartrate

Unirradiated ammonium tartrate (AT) samples do not exhibit any ESR signal. However, irradiation produces an unresolved singlet at g=2.0034±0.0006 with two shoulders at g₁=2.0093±0.0006 and g₂=2.0048±0.0006. The dose–response curve was found to increase linearly with the applied radiation doses in the range of 0.1–2.0 kGy and the slope of this curve was increased as the modulation amplitude increased. The activation energy value E_a=69.0±1.2 kJ/mol was calculated from Arrhenius plot for the radical species responsible from ESR spectrum of irradiated AT.     

Hindered rotation of methylene groups in irradiated zinc acetate dihydrate: a double modulation ESR study

Hindered rotational motion of methylene groups in irradiated zinc acetate has been studied by the double modulation ESR technique. Two excited levels, at E₀ = 6.7 ± 0.6 kJ mol⁻¹ and E_j = 18.4 ± 1.0 kJ mol⁻¹, corresponding respectively to the torsional oscillation and full Jump rotation of the methylene group, were determined.     

Using ESR spectroscopy to study radical intermediates in proton-exchange membranes exposed to oxygen radicals

Direct ESR and spin-trapping experiments were used to study the behavior of Nafion, a perfluorinated ionomer membrane used in fuel cells, when exposed in the laboratory to oxygen radicals produced by Fenton and photo-Fenton reactions. DMPO (5,5-dimethyl-1-pyroline) was used as the spin trap. The results suggest that the two ESR methods provide complementary information on Nafion fragmentation. The presence of membrane-derived fragments was suggested indirectly by the presence of a broad signal (line width ≈ 84 G) after prolonged exposure of the membrane to the Fenton reagent based on Ti(III), and by the DMPO adduct of a carbon-centered radical in the spin-trapping experiments. The most convincing proof for the presence of perfluorinated radicals was obtained in Nafion membranes partially neutralized by Cu(II), Fe(II) and Fe(III) upon exposure to UV-irradiation in the presence or absence of H₂O₂ (photo-Fenton treatment). Identification of the chain-end radical RCF₂CF ₂ ^• with magnetic parameters different to those determined for the chain-end detected in γ-irradiated Teflon, was taken as evidence for the attack of reactive oxygen radicals on the side-chain of the membrane. Additional support for this suggestion was the detection of the “quartet” ESR signal assigned to the CF₃C^•O radical, and of the “quintet” ESR signal assigned to the radical centered at the intersection of the main and side chains. The limitations and advantages of each approach are discussed.     

配位聚合载体化催化剂ESR研究进展

本文概述了配位聚合载体化催化剂的ESR研究进展,介绍了载体研究、活性中心研究及计算机模拟技术研究方面的发展概况.     

ESR study of hypercrosslinked polystyrene carbonizate—organic solvent—oxygen systems

Carbonizates of hypercrosslinked polystyrenes were studied by ESR spectroscopy. Conditions for preparation of paramagnetic carbon sorbents used as oxygen sensors were determined. These sorbents are characterized by an intense narrow ESR singlet for air desorption by pyridine, glycerol, ethanol, methanol, and water. For the carbonizates of nonionogenic biporous hypercrosslinked polystyrenes (I) or sulfonic cation-exchange resins based on biporous hypercrosslinked polystyrenes (II), the ESR line width decreases from 10 G in oxygen to 0.4–1.2 G (0.4 G for glycerol) upon solvent introduction, and the signal amplitude increases by two-three orders of magnitude. When solvents with the linear structure of molecules (alkanes, their mono-and dichlorosubstituted derivatives, alcohols) are introduced, the ESR line can decrease to 2.3±0.3 G. Carbonizates I and II obtained by pyrolysis at temperatures 580–620 °C possess a large internal surface (up to 680 m² g⁻¹) and contain packets of condensed aromatic polycycles with delocalized π-electrons. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 824–831, May, 2006.     

Identification of irradiated sage tea (Salvia officinalis L.) by ESR spectroscopy

The use of electron spin resonance (ESR) spectroscopy to accurately distinguish irradiated from unirradiated sage tea was examined. Before irradiation, sage tea samples exhibit one asymmetric singlet ESR signal centered at g=2.0037. Besides this central signal, two weak satellite signals situated about 3 mT left and right to it in radiation-induced spectra. Irradiation with increasing doses caused a significant increase in radiation-induced ESR signal intensity at g=2.0265 (the left satellite signal) and this increase was found to be explained by a polynomial varying function. The stability of that radiation-induced ESR signal at room temperature was studied over a storage period of 9 months. Also, the kinetic of signal at g=2.0265 was studied in detail over a temperature range 313–353 K by annealing samples at different temperatures for various times.     

ESR Study of Trimethylsilane Plasma Polymer Part II; Effect of Consecutive Treatments and Mixed Gases

An ESR study has indicated that a second plasma treatment on plasma deposited films from trimethylsilane (TMS) monomer gas has the ability to modify the characteristics of the primary plasma polymer significantly in a favorable manner for many applications. The effect of the second plasma polymerization on the primary plasma polymer of TMS depends on the nature of the second monomer. Plasma of F-containing monomer, hexafluoroethane (HFE) and perfluoromethane (CF₄), decreases the ESR signal of TMS and no detectable signal due to F-containing monomer was found. The decay rate of the signal decreased significantly. In contrast to this situation, CH₄ plasma treatment yields an ESR signal that is a composite of that observed from TMS and CH₄ films individually. The overall signal increased in this instance, but didn't show appreciable decay in 24 hr period. A second treatment by nonpolymer forming plasmas also decreased the ESR signal of TMS, and decreased the decay rate, indicating that the second gas plasma treatment yields a somewhat similar effect found with the HFE plasma treatment. Plasma polymerization of mixtures of TMS and nonpolymer-forming gases increased the ESR signal but decreased the decay rate, except in the case of oxygen. A mixture of (TMS + O₂) behaved as a completely different monomer. No ESR signal was found in this system. The ESR analysis was supported by XPS data and an insight into the mechanisms occurring in these thin films are discussed.     

Conformational Study by ESR. of Some Alkyl Substituted 6a-Thiathiophthene Radical Anions

ESR. data are reported for the radical anions (II^? to VI^?) of five alkyl substituted 6a-thiathiophthenes. Rates and activation parameters for the inversion of the 3,4-trimethylene chain in IV^?, V^? and VI^? have been obtained by means of an iterative least squares computer program ESRCEX. Preferential conformations of the alkyl substituents are discussed in terms of the 〈cos²θ〉 dependence of the β-proton coupling constants and with the aid of molecular models. Experimental evidence strongly suggests that the partial rotation of the ethyl and isopropyl groups in V^? and VI^? is correlated with the inversion of the 3,4-trimethylene chain.     

Definitive evidence that the ESR spectrum observed during photolysis of Mn2(CO)10 in THF is due to octahedral high-spin (d5) manganese(II)

The reassignment to a manganese(0) quartet state by C.L. Kwan and J.K. Kochi (J. Organometal. Chem., 101 (1975) C9) of the ESR spectrum obtained during photolysis of Mn₂(CO)₁₀ in THF is shown to be in error; computer simulation of the X-band spectrum and observation of the S-band spectrum confirm our previous assignment to sextet manganese(II) and chemical and IR evidence indicate the presence of [Mn(CO)₅]^? as a counter ion.     

ESR study of nitro-substituted iminoxyl radicals

Iminoxyl radicals involved in the homolytic oxidation of nitrolic acids, with the general formula (NO₂)RC=NO^., have been detected by means of ESR. In the presence of a strong acid, the ESR spectra of the radical (NO₂)₂C=NO^. exhibits alternation of the line widths, owing to syn-anti isomerization.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1513–1516, July, 1991.