Characterization of ancient and modern papers by CW-EPR spectroscopy

Several old (15th to 18th century), new (1900–1950) and recently produced (after 1990) papers have been investigated by X-band continuous-wave electron paramagnetic resonance (EPR) spectroscopy. Signals from Cu(II), Fe(III), Mn(II) and radicals are apparent. A clear-cut distinction is observed between recently produced papers and the other samples: recent papers show just EPR signals from Mn(II) and sometimes small signals from Fe(III) in rhombic site, while the older samples show usually strong signals from Fe(III), Mn(II), Cu(II) and radicals. Furthermore, Mn(II) EPR signals from recent papers are characterized by small zero-field splitting (ZFS) parameters, indicating Mn(II) in high-symmetry sites, while older samples show broader Mn(II) EPR signals, typical for Mn(II) in low-symmetry sites (increased ZFS parameters).     

A review of spin Hamiltonians applicable to exchange-coupled systems of interest in biomaterials

Dinuclear and tetranuclear complexes of spin-coupled manganese-manganese, manganese-iron, and iron-iron ions occur in enzymes which are of importance in biology and photosynthesis. These multinuclear systems contain higher oxidation states of manganese and iron ions than those of the commonly occurring Mn(II) and Fe(III) mononuclear ions, in which there has been a lot of interest recently with regard to their electron paramagnetic resonance (EPR) spectra. In order to aid the interpretation of EPR spectra, the spin Hamiltonians, and the resulting energy levels, characterizing binuclear and tetranuclear manganese ions will be discussed in this presentation. These will include, in particular, Mn(II)?Mn(III), Mn(III)?Mn(IV), and Mn(IV)?Mn(V) systems for the binuclear situation, and the Mn₄O₂ “butterfly”, cubane, dimer of dimer systems, and diamond structure for the tetramer situation. These coupled systems are characterized by a variety of exchange interactions whose magnitudes and nature, ferromagnetic or antiferromagnetic, affect profoundly the energy levels. In addition, the hyperfine interactions amongst the various⁵⁵Mn nuclei produce a complex EPR spectrum consisting of a large number of hyperfine lines. In order to interpret EPR spectra properly, one needs to simulate them as accurately as possible. Details of a rigorous technique for the simulation of EPR spectra of these systems with matrix diagonalization and homotopy technique will be provided.     

The Role of Metal Ions in the Study of Ancient Paper by Electron Paramagnetic Resonance

Samples from covers and endleaves of sixteenth to eighteenth century books in good conservation state from the Biblioteca Nazionale Marciana in Venice have been investigated by means of electron paramagnetic resonance (EPR) spectroscopy and optical microscopy to characterize the embedded paramagnetic species and to test differences and similarities of the materials in the two types of book components. We detected the Mn(II), Fe(III), and Cu(II) paramagnetic ions, and analyzed their EPR signals by comparing them with previous results in literature of EPR studies on paper. Interestingly, the Mn(II) EPR spectrum profile appears as a fingerprint for samples coming from the same book, either from cover or endleaf, and it looks different for samples extracted from different books. We discuss the role of EPR as a spectroscopic tool for characterizing the interaction of the ions with the paper components and as possible agents of degradation.     

EPR Studies of DOPA–Melanin Complexes with Fe(III)

Paramagnetic centers in 3,4-dihydroxyphenylalanine–melanin and its complexes with Fe(III) were examined by electron paramagnetic resonance (EPR) spectroscopy. Paramagnetic centers of melanin play an important role in detoxification of environment and they reveal high activity in binding of metal ions. Two different signals were observed in EPR spectra: lines of o-semiquinone free radicals and lines of paramagnetic Fe(III). Amplitudes of EPR lines of both free radicals and iron ions decrease with increasing Fe(III) content in melanin–metal ion complexes. Free radical concentrations in the melanin samples, g-factors, amplitudes and line widths of EPR spectra were determined. It was stated that fast spin–lattice relaxation processes exist in both free radical system and paramagnetic iron ions in melanin complexes.     

Phenomena associated with diffusion of trivalent iron in amethyst quartz

In natural amethyst crystals from different locations changes in the EPR, optical and infrared spectra were measured as a function of annealing temperature. After heating to 650°C for two hours the concentration of Fe(III) on substitutional sites with alkali ions as charge compensators is equal in all crystals irrespective of its initial concentration. Establishment of a heterogeneous equilibrium due to formation of iron oxide particles (presumably Fe₂O₃) previously characterized by their EPR and optical spectra is thus confirmed. Initially unequal distributions of Fe(III) among the three equivalent sites of the quartz structure also become equal under this treatment. From comparison with literature data for MnCl₂ precipitates in NaCl the average particle size can be estimated to be about 100 nm allowing an estimate of the diffusion coefficient of Fe(III) at 650°C. In one amethyst with a high concentration of hydrogen a large amount of the substitutional Fe(III) is charge compensated by hydrogen. Thermal destruction of these centers does not correlate with the intensities of infrared absorption bands in the OH stretching vibration region.     

Characterization of Phyllanthus amarus herb by inductively coupled plasma mass spectrometric (ICP-MS) analysis,optical absorption and electron paramagnetic resonance (EPR) spectroscopic methods

A powdered sample of Phyllanthus amarus herb of Kadapa district of Andhra Pradesh, India, is used in the present study. ICP-MS analysis indicates that copper is present in higher concentration when compared to other elements. Although the Pb is toxic, it is within the permissible limit. The evaluated soil and herb physico-chemical parameters indicate that the sample is acidic in nature in comparison with the soil. An EPR study on powdered sample confirms the presence of Fe(III), Mn(II) and Cu(II). Optical absorption spectrum indicates that Fe(III) impurity is present in octahedral structure whereas Cu(II) is present in rhombically distorted octahedral environment. MIR results are due to carbonate fundamentals.     

EPR of the first Fe(III)-containing spin-crossover metallomesogens

The low-spin (LS) to high-spin (HS) transition in two mesogenic Fe(III) complexes with alkyloxysalicyliden-N^′-ethyl-N-ethylendiamine as ligands is studied by electron paramagnetic resonance (EPR). The symmetrization of the crystal field around the Fe(III) ion under first heating of a polycrystalline sample from the room temperature was observed in the spectra of HS complexes. The line narrowing (from 45 to 15 mT) under the crystal-smectic phase transition is explained by the strengthening of the intermolecular exchange interaction, as a result of the structural reorganization of layers in the smectic phase. A feature of both mesogenic spin-transition systemsis an unusual field-induced spin instability which leads to the hysteresis of the HS-LS composition. This instability is detected by EPR and magnetic susceptibility methods. The alignment of systems by magnetic field in the mesophase and a complete or partial orientational order under cooling the mesophase to the glass state are the main reason for this hysteresis. The influence of EPR-silent LS complexes reveals itself in the line broadening of HS compounds’ when the temperature is lowered from 220 K.     

EPR Monitoring of BaTiO<Subscript>3</Subscript> Formation

BaCO₃ and anatase-type TiO₂ were adopted as initial materials to prepare BaTiO₃ powder by the solid-state reaction method at a heating rate of 350°C/h. The electron paramagnetic resonance (EPR) technique was employed to monitor the formation of BaTiO₃. TiO₂ showed a series of complicated EPR signals associated primarily with Fe impurities. The formation of BaTiO₃ can be monitored in terms of the evolution of EPR signals associated with Fe impurities with calcination and measurement temperatures. The activation of the g = 2.004 signal above the Curie point of BaTiO₃ and the disappearance of the other EPR signals in the BaCO₃/TiO₂ mixture at room temperature are characteristic of the formation of BaTiO₃.     

Studies of Nanosized Iron-Doped TiO<Subscript>2</Subscript> Photocatalysts by Spectroscopic Methods

Iron-doped TiO₂ nanoparticles with iron content in the range of 0.005 < Fe/Ti < 0.3 were prepared using the flame spray pyrolysis method and investigated with CW X-band electron paramagnetic resonance (EPR), X-ray diffraction, and Fourier transform infrared spectroscopy. This allowed for the clarification of the internal organization of Fe–TiO₂ nanoparticles. Different types of Fe(III) centers were distinguished in the samples: isolated high-spin paramagnetic Fe(III) ions (S = 5/2) in rhombic ligand fields state at 0.005 < Fe/Ti < 0.05, and Fe(III) ferromagnetic clusters at Fe/Ti < 0.1. All Fe-doped samples had rather high activity for the photocatalytic mineralization of oxalic acid under visible light illumination (λ > 400 nm) at 25 °C. Correlations were made between EPR and photocatalytic activity results. The specific surface area [S] data allowed us to deduce that the isolated Fe(III) centers were responsible for the photomineralisation of oxalic acid, while the Fe(III) ferromagnetic aggregates decreased the total efficiency of the system.     

Mössbauer Study of Nanocrystalline ε-Fe3−x Co x N System

Five clays from four different deposits in the Ivory Coast (Adattié, Nieki, Grand-Bassam, Nigui-Saff) were studied by ⁵⁷Fe Mössbauer spectroscopy and electron paramagnetic resonance (EPR) at room temperature. Their chemical compositions were determined by X-ray fluorescence and the most important crystalline phases were identified by X-ray diffraction. In these natural clays, kaolinite is the dominant mineral phase with minor amounts of other minerals including quartz, haematite, goethite, lepidocrocite and illite. Room-temperature ⁵⁷Fe Mössbauer spectra of the samples from Nieki, Adattié and Nigui-Saff show mainly a broad quadrupole-split doublet which indicates that iron is essentially present as Fe(III). Samples from Grand-Bassam contain important amounts of goethite (α-FeOOH) and lepidocrocite (γ-FeOOH). Some samples from Nigui-Saff contain large amounts of haematite. Clays from Nieki and Adattié are characterised by very low concentrations of iron oxides or hydroxides, and by small amounts of structural Fe(II) in the kaolinite lattice. Oxidation states and lattice sites of structural iron in the kaolinites were determined by ⁵⁷Fe Mössbauer spectra recorded after iron extraction with dithionite-citrate-bicarbonate (DCB). The results were confirmed by electron paramagnetic resonance (EPR) measurements.     

Effect of heat treatment and concentration of Mn and Fe on the structure of borate glass

We have studied the magneto-optic Faraday effect (FE) and electron paramagnetic resonance (EPR) in an aluminum potassium borate glass containing Fe oxides as an impurity in a concentration of 1.5 mass % and Mn impurity in variable concentration from 0 to 1.2 mass %. When manganese oxide is added to the glass composition, the paramagnetic contribution to the Faraday effect increases more slowly than the change in the total concentration of paramagnetic ions, which allows us to hypothesize the appearance of clusters in which the paramagnetic ions are coupled by antiferromagnetic interactions. Formation of clusters upon addition of manganese oxide is confirmed by the change in the nature of the EPR spectra, where we observe a manganese concentration dependence of the distribution of iron atoms with respect to the different positions in the glass matrix. Heat treatment leads to a strong increase in the Faraday effect and a change in the spectral dependences of the Faraday effect and the EPR, which is explained by enlargement of the clusters and appearance of nanoparticles. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 3, pp. 354–358, May–June, 2006.     

Study of microimpurities and charge states in homogeneous hydrocarbon films (Redeposited from a T-10 tokamak deuterium plasma discharge) using XRF analysis, IR spectroscopy, EPR, and I-V characteristics

Microimpurities and charge states of homogeneous deuterated hydrocarbon films redeposited from a T-10 tokamak deuterium plasma discharge are studied spectroscopically using x-ray fluorescence (XRF) analysis, electron paramagnetic resonance (EPR), infrared (IR) spectroscopy; current-voltage (I-V) charachteristics are also measured. Twelve microimpurities (mainly, those of transition metals Fe, Mo, Cr, Ni, Ti, etc., with relative concentrations of 50–7000 ppm) have been discovered. The resulting broad EPR (9.9 GHz, 6000 G) line with g-factors of g = 2.053–2.093 and g = 4.3 assigned to paramagnetic impurities confirms their presence. The presence of different charge states on two sides of the film (one facing the plasma and another facing the vacuum-chamber wall) and the difference in the IR spectra of these states are established. This can be explained by the process of film formation under the influence of the tokamak plasma.     

A Calibration Reaction for Rapid Freeze-Quench W-Band EPR

A simple setup for rapid freeze-quench electron paramagnetic resonance (EPR) at W-band is described. It is based on a BioLogic commercial apparatus and a modified sample collection appropriate for W-band capillaries. The standard reaction of myoglobin with azide, which converts high-spin Fe(III) to low-spin Fe(III), used for calibration of rapid freeze-quench X-band EPR is very inconvenient for high-field measurements. Here we propose a different simple calibration reaction for W-band: the reduction of a nitroxide free radical with sodium dithionite using Mn²⁺ as an internal standard. Using this calibration reaction we determined the dead time of our system to be less than 10 ms.     

光合作用水裂解机理与EPR应用研究

在绿色植物放氧光合作用中,光系统II（PSII）催化着自然界利用光能将水裂解并释放出氧气的化学反应. 在研究PSII的生物催化机理中,电子顺磁共振（EPR）波谱学发挥着非常重要的作用. 该文综述了与水裂解有关的EPR应用研究,如锰簇Mn₄O₅Ca的不同氧化中间态,以及这些不同氧化态的锰簇与酪氨酸Y-Z自由基的磁性相互作用等,这些进展揭示了水裂解过程是一个逐步的与质子耦联的电子传递过程.     

Mössbauer spectroscopy for optimising systems for environmental remediation

Mössbauer spectroscopy was used to examine Fe-containing microporous materials zeolite X and AlPO-5 designed for the reduction of Cr(VI) to Cr(III) and Cr(III) uptake. XRD, XRF, EPR and XPS were used to provide supporting information. AlPO-5 was found to only incorporate inactive Fe(III), whilst Fe(II) and Fe(III) were identified in zeolite X across a distribution of sites. Fe coordinates to oxygen atoms belonging to both water molecules and framework positions. EPR confirmed these findings and showed how the site distribution narrows upon dehydration. XPS showed that a distribution of Fe sites exists at the sample surface. Mössbauer spectroscopy was also used to track oxidation and reduction processes in Fe-zeolite X. Over time, gradual Fe oxidation takes place in air-exposed samples. Reduction under hydrogen flow increases the populations of low oxidation state Fe; as the reaction time increases, Fe(II) populations first increase, then decrease as Fe(0) is evolved.     

An EPR Study on the Chemical form of Mn2+ in the Chinese Loess Samples

Electron paramagnetic resonance (EPR) spectroscopy in combination with thermal methods were used to identify and characterize Mn²⁺ in the Chinese loess that is a multimineral system. EPR spectra of the loess samples from the classic loess-paleosol section in central China show the presence of trace amounts of Mn²⁺; whereas paleosol samples present no Mn²⁺ EPR signal. The spectral changes upon step heating from room temperature to 1000 °C suggest that this EPR signal in the loess arises from Mn substituted into CaCO₃. This study provides a direct evidence that the loess-paleosol profiles were formed under the changing redox conditions caused by a past climatic change.     

EPR study of Mn2+ doped nanocrystalline PbF2

Nanocrystalline samples of PbF2 doped with 0.05, 0.1, 0.4 and 1 mol% Mn2+, used as paramagnetic probe, were prepared by inert gas condensation technique. All the samples were vacuum annealed at different temperatures to get different grain sizes. The X-ray diffraction studies showed the dominant content of -PbF2 phase with a fractional quantity of -PbF2. Thermal stability and sublattice melting were studied by TGA and DSC respectively. EPR measurements were made on all these samples at 77 and 300 K. The EPR spectra of all samples were found to contain well resolved sextet arising from the Mn2+ ions that occupied the cubic sites of Pb2+ ion of PbF2 lattice. The lower concentration of the Mn2+ ions (0.05 and 0.1 mol%) clearly monitored the Pb2+ environment in the PbF2 lattice. The 0.4 mol% showed the presence of only the cubic sites with a minor concentration of the orthorhombic sites. The spectra corresponding to 1 mol% Mn2+ clearly showed two different components. The isotropic nature of the 1 mol% as-prepared sample implied that there was no cluster formation and hence this EPR spectrum was taken as the single ion spectrum. The annealed samples contain two spectral components; one is from the isolated single ions and the other one from the Mn2+ clusters. The spectral component of Mn2+ clusters was obtained by subtracting the spectrum for the as-prepared sample for the spectra of annealed samples. The extracted cluster phase spectra and the pure spectrum from the as-prepared sample were then combined to simulate the entire set of experimental spectra. The simulated spectra were found to be in good agreement with the experimental data. The g values obtained were in the range very close to the free electron g factor as the electrons are in the S state (L=0).     

Tunable-frequency high-field electron paramagnetic resonance

A tunable-frequency methodology based on backward wave oscillator sources in high-frequency and -field EPR (HFEPR) is described. This methodology is illustrated by an application to three non-Kramers transition metal ion complexes and one Kramers ion complex. The complexes are of: Ni(II) (S=1) as found in dichlorobistriphenylphosphanenickel(II), Mn(III) (S=2) as found in mesotetrasulfonatoporphyrinatomanganese(III) chloride, Fe(II) (S=2) as found in ferrous sulfate tetrahydrate, and Co(II) (S=3/2) as found in azido(tris(3-tert-butylpyrazol-1-yl)hydroborate)cobalt(II). The above Ni(II) and Mn(III) complexes have been studied before by HFEPR using the multifrequency methodology based on Gunn oscillator sources, but not by the present method, while the Fe(II) and Co(II) complexes presented here have not been studied by any form of HFEPR. Highly accurate spin Hamiltonian parameters can be obtained by the experimental methodology described here, in combination with automated fitting procedures. This method is particularly successful in determining g-matrix parameters, which are very difficult to extract for high-spin systems from single frequency (or a very limited set of multi-frequency) HFEPR spectra, but is also able to deliver equally accurate values of the zero-field splitting tensor. The experimental methods involve either conventional magnetic field modulation or an optical modulation of the sub-THz wave beam. The relative merits of these and other experimental methods are discussed.     

Ti：Al2O3晶体的电子自旋共振谱研究

Ｔｉ：Ａｌ２Ｏ３晶体中的顺磁中心Ｔｉ＾３＋由于强烈的晶格自旋耦合而使其电子自旋共振吸收只有在液拟温度附近才能看到，本实验在液氮温度附近记录到由许多强的的吸收峰迭加于Ｔｉ＾３＋宽吸收线所组成的电子自旋共振谱，这些吸吸收峰被认为是Ａｌ２Ｏ３基质中的Ｆｅ＾３＋，Ｍｎ＾２＋，Ｃｒ＾３＋，Ｍｏ＾３＋，Ｆｅ＾２＋，Ｃｏ＾２＋等杂质的共振吸收及Ｔｉ＾２＋３Ａ２ｇ基态的双量子跃迁造成的。     

Probing electronic and structural properties of the reduced [2Fe−2S] cluster by orientation-selective1H ENDOR spectroscopy: Adrenodoxin versus rieske iron-sulfur protein

The¹H electron-nuclear double resonance (ENDOR) spectra in frozen buffer solutions of the reduced [2Fe?2S] clusters in adrenodoxin (Adx) and in the “Rieske” iron-sulfur protein (ISP) from the bovine mitochondrial bc1 complex were measured at low temperatures (5–20 K) and analyzed by spectra reconstruction. A single paramagnetic species with iron valence states (II) and (III) connected uniquely to the cluster irons was found in both proteins. For Adx, the experimental spectra from 23 field positions across the nearly axial (g _max=2.0241,g _int=1.9347, andg _min=1.9331) electron paramagnetic resonance (EPR) spectrum were analyzed. Four larger hyperfine couplings were assigned to the cysteine β-protons near the Fe(III) ion. Transfer into the crystal structure showed that the Fe(III) ion was coordinated to the residues Cys55 and Cys92. The spin density was estimated as +1.60 for the Fe(III) and ?0.6 for the Fe(II) ion, respectively. Theg-tensor direction with respect to the cluster showed strong similarities with the earlier assignment inArthospira platensis ferredoxin (Canne C., Ebelshauser M., Gay E., Shergill J.K., Cammack R., Kappl R., Hüttermann J.: J. Biol. Inorg. Chem. 5, 514, 2000). An Adx mutant (T54A) exhibiting a change (70 mV) in redox potential showed no significant influence at the [2Fe?2S] cluster. The Rieske ISP was subjected to the same analysis. The ENDOR spectra from 35 field positions across the rhombic (g _max=2.028,g _int=1.891, andg _min=1.757) EPR spectrum were simulated. Three major proton contributions were identified from the orientation behavior. Two were assigned to cysteine β-protons and one to a β-proton of His141. In contrast to Adx, the direction of theg _max-component was found to lie roughly in the FeS-core plane and the largest proton coupling occurred alongg _int. The spin population was estimated as about +1.6 for the oxidized and ?0.55 for the reduced iron.