Local defect structures and EPR studies on (FeO6)9− and (FeO4)5− clusters in YGG: Fe3+ system

The octahedral (FeO₆)^9? and tetrahedral (FeO₄)^5? clusters in yttrium gallium garnet (YGG): Fe³⁺ system are investigated based on the 252 × 252 complete energy matrices for d⁵ configuration ions in trigonal and tetragonal ligand fields, moreover, the EPR and optical spectra are made unified calculation. The results indicate that the defect structures around Fe³⁺ centres display expansion effects at different temperatures 4.2 and 295 K, and which are close to those in YIG garnet, respectively. Simultaneously, the defect structure parameters for Fe³⁺ centres in YGG are determined, and the relationship between the defect structure and the temperature has been discussed.     

Identification of radical structures on 1‐pentamethylbenzyl‐3‐ethylimidazoliumsilver(I)bromide and 1,3‐bis(pentamethylbenzyl)‐4,5‐dimethylbenzimidazoliumsilver(I)bromide exposed to gamma rays: an EPR study

1‐Pentamethylbenzyl‐3‐ethylimidazoliumsilver(I)bromide and 1,3‐bis(pentamethylbenzyl)‐4,5dimethylbenzimidazoliumsilver(I)bromide and their Ag⁺ complexes were synthesized and their polycrystal forms were produced by recrystallization in dichloromethane/Et₂O solvent system. Structural determinations were carried out by ¹H NMR and ¹³C NMR with a Varian 400 NMR system using tetramethylsilane as internal standard and CDCl₃ as solvent. The disappearance of acidic N‐heterocyclic carbene proton showed the formation of Ag(I) complexes. Also, elemental analyses were carried out. Electron paramagnetic resonance (EPR) measurements were performed to determine the formed radical structure on the samples irradiated at the room temperature for 72 h by using ⁶⁰Co‐source with dose rate of 0.680 kGy. The EPR measurements were carried out in the temperature range of 200 K–450 K. Identical radicals were determined on the irradiated compounds. It was observed that the shapes of the spectra of the samples were independent of the temperature but, the resonance line intensities changed linearly with the temperature. Also, it was detected that the free radical on the 1‐pentamethylbenzyl‐3‐ethylimidazoliumsilver(I)bromide is not stable compared to that on the 1,3‐bis(pentamethylbenzyl)‐4,5dimethylbenzimidazoliumsilver(I)bromide. Copyright © 2016 John Wiley & Sons, Ltd.     

EPR,ENDOR and optical spectroscopy of Yb3+ ion in KZnF3 single crystals

The paramagnetic center of tetragonal symmetry formed by the Yb³⁺ ion in the KZnF₃ crystal has been studied using methods of EPR, ENDOR and optical spectroscopy. The location of the impurity ion and the structural model of the complex differing from the model of the Yb³⁺ center in KMgF₃ have been established. The empirical scheme of the energy levels of the Yb³⁺ ion has been found. The parameters of its interaction with the crystal electrostatic field and the hyperfine interaction with ligands of the nearest environment have been determined. The parameters of the crystal field were used for the analysis of the distortions of the crystal lattice in the vicinity of Yb³⁺. The parameters of the transferred hyperfine interaction have been calculated for the distances between Yb³⁺ and F⁻ ions of the nearest environment obtained taking into account the found distortions. They are in good agreement with the experimental values.     

A Rapid Freeze‐Quench Setup for Multi‐Frequency EPR Spectroscopy of Enzymatic Reactions

Electron paramagnetic resonance (EPR) spectroscopy in combination with the rapid freeze‐quench (RFQ) technique is a well‐established method to trap and characterize intermediates in chemical or enzymatic reactions at the millisecond or even shorter time scales. The method is particularly powerful for mechanistic studies of enzymatic reactions when combined with high‐frequency EPR (ν≥90 GHz), which permits the identification of substrate or protein radical intermediates by their electronic g values. In this work, we describe a new custom‐designed micro‐mix rapid freeze‐quench apparatus, for which reagent volumes for biological samples as small as 20 μL are required. The apparatus was implemented with homemade sample collectors appropriate for 9, 34, and 94 GHz EPR capillaries (4, 2, and 0.87 mm outer diameter, respectively) and the performance was evaluated. We demonstrate the application potential of the RFQ apparatus by following the enzymatic reaction of PpoA, a fungal dioxygenase producing hydro(pero)xylated fatty acids. The larger spectral resolution at 94 GHz allows the discernment of structural changes in the EPR spectra, which are not detectable in the same samples at the standard 9 GHz frequency.     

RGD-conjugated triarylmethyl radical as probe for electron paramagnetic imaging

A stable RGD-conjugated triarylmethyl (TAM) radical 3 has been synthesized in a straightforward three-step sequence. CT-03 ‘the Finland trityl’ which is a very popular contrast agent for electron paramagnetic resonance imaging has been covalently bound to the NH₂-ending of a pentapeptide commonly used to target integrins and confers tissue selectivity. Moreover, this new TAM radical is stable and sensitive to molecular oxygen.