Room temperature Q-band electron magnetic resonance study of radicals in X-ray-irradiated l-threonine single crystals.

In the past, decennia radiation-induced radicals were successfully identified by electron magnetic resonance (EMR) in several solid-state amino acids and sugars. The authors present a room temperature (RT) EMR study of the stable radicals produced by X-ray-irradiation in the amino acid l-threonine (CH3CH(OH)CH(NH3 (+))COO(-)). Its chemical structure is similar to that of the well-known dosimetric material l-alanine (CH3CH(NH3(+))COO(-)), and radiation defects in l-threonine may straightforwardly be compared with the extensively studied l-alanine radicals. The hyperfine coupling tensors of three different radicals were determined at RT using electron nuclear double resonance. These results indicate that the two most abundant radicals share the same basic structure CH3(•)C(OH)CH(NH3(+))COO(-), obtained by H-abstraction, but are stabilised in slightly different conformations. The third radical is most probably obtained by deamination (CH3CH(OH)(•)CHCOO(-)), similar in structure to the stable alanine radical.

Synthesis, characterization and sorption properties of NH2-MIL-47.

An amino functionalized vanadium-containing Metal Organic Framework, NH(2)-MIL-47, has been synthesized by a hydrothermal reaction in an autoclave. Alternatively, a synthesis route via microwave enhanced irradiation has been optimized to accelerate the synthesis. The NH(2)-MIL-47 exhibits the same topology as MIL-47, in which the V center is octahedrally coordinated. After an exchange procedure in DMF the V(+III) center is oxidized to V(+IV), which is confirmed by EPR and XPS measurements. The CO(2) and CH(4) adsorption properties have been evaluated and compared to MIL-47, showing that both MOFs have an almost similar adsorption capacity and affinity for CO(2). DFT-based molecular modeling calculations were performed to obtain more insight into the adsorption positions for CO(2) in NH(2)-MIL-47. Furthermore our calculated adsorption enthalpies agree well with the experimental values.

Radiation-induced radicals in glucose-1-phosphate. II. DFT analysis of structures and possible formation mechanisms.

Four radiation-induced carbon-centered radicals in dipotassium glucose-1-phosphate dihydrate single crystals are examined with DFT methods, consistently relying on a periodic computational scheme. Starting from a set of plausible radical models, EPR hyperfine coupling tensors are calculated for optimized structures and compared with data obtained from EPR/ENDOR measurements, which are described in part I of this work. In this way, an independent structural identification is made of all the radicals that were observed in the experiments (R1-R4) and tentative reaction schemes are proposed. Also, the first strong evidence for conformational freedom in sugar radicals is established: two species are found to have the same chemical composition but different conformations and consequently different hyperfine coupling tensors. Analysis of the calculated energies for all model compounds suggests that the radiation chemistry of sugars, in general, is kinetically and not necessarily thermodynamically controlled.

Radiation-induced radicals in glucose-1-phosphate. I. Electron paramagnetic resonance and electron nuclear double resonance analysis of in situ X-irradiated single crystals at 77 K.

Electron magnetic resonance analysis of radiation-induced defects in dipotassium glucose-1-phosphate dihydrate single crystals in situ X-irradiated and measured at 77 K shows that at least seven different carbon-centered radical species are trapped. Four of these (R1-R4) can be fully or partly characterized in terms of proton hyperfine coupling tensors. The dominant radical (R2) is identified as a C1-centered species, assumedly formed by a scission of the sugar-phosphate junction and the concerted formation of a carbonyl group at the neighboring C2 carbon. This structure is chemically identical to a radical recently identified in irradiated sucrose single crystals. Radical species R1 and R4 most likely are C3- and C6-centered species, respectively, both formed by a net hydrogen abstraction. R3 is suggested to be chemically similar to but geometrically different from R4. Knowledge of the identity of the sugar radicals present at 77 K provides a first step in elucidating the formation mechanism of the phosphoryl radicals previously detected after X-irradiation at 280 K. In paper II, the chemical identity, precise conformation, and possible formation mechanisms of these radical species are investigated by means of DFT calculations and elementary insight into the radiation chemistry of sugar and sugar derivatives is obtained.

Multifrequency electron paramagnetic resonance study on deproteinized human bone.

Irradiated samples of deproteinized powdered human bone (femur) have been examined by electron paramagnetic resonance (EPR) spectroscopy in X, Q and W bands. In the bone powder sample only one type of CO2- radical ion is stabilized in the hydroxyapatite structure in contrast to powdered human tooth enamel, a material also containing hydroxyapatite, widely used for EPR dosimetry and in which a few radicals are stable at room temperature. It is suggested that the use of deproteinized bone for EPR dosimetry could improve the accuracy of dose determination.

Q-band EPR and ENDOR of low temperature X-irradiated beta-D-fructose single crystals.

Beta-D-fructose single crystals were in situ X-irradiated at 80 K and measured using electron paramagnetic resonance (EPR), electron nuclear double resonance (ENDOR) and ENDOR-induced EPR (EIE) techniques at Q-band (34 GHz) microwave frequencies. The measurements revealed the presence of at least four carbon-centered radicals stable at 80 K. By means of ENDOR angular variations in the three principal crystallographic planes, six proton hyperfine coupling tensors could be determined and were assigned to four different radicals by the aid of EIE. Two of the radicals exhibit only beta-proton hyperfine couplings and reveal almost identical EIE spectra. For the other two radicals, the major hyperfine splitting originates from a single alpha-proton hyperfine coupling and their EIE spectra were also quite similar. The similarity of the EIE spectra and hyperfine tensors led to the assumption that there are only two essentially different radical structures. The radical exhibiting only beta-proton hyperfine couplings was assigned to a C3 centered radical arising from H3 abstraction and the other radical suggested to be an open-ring species with a disrupted C2-C3 bond and a double C2-O2 bond. A possible formation mechanism for the latter open-ring radical is presented. By means of cluster density functional theory (DFT) calculations, the structures of the two radicals were determined and a fairly good agreement between the calculated and experimental hyperfine tensors was found.

Attempts at correlation of the radiolytic species of irradiated solid-state captopril studied by multi-frequency EPR and HPLC.

The purpose of this study was to provide insight into the processes that occur after the irradiation of solid-state drugs. Electron paramagnetic resonance (EPR) experiments were performed at two different frequencies, X-band (about 9.5 GHz) and Q-band (about 34 GHz), to identify the radicals present in irradiated captopril. The results confirmed that an irradiated drug can trap several main radicals. Moreover, the radical composition varied as a function of the treatment. In addition, non-volatile final products were studied by liquid chromatography coupled to UV and to mass spectrometry (LC-MS). The variation of the radical composition did not influence the profile of the final products; this appears to indicate that, in the case of captopril, the trapped radicals observed by EPR are not the main precursors of the final products. Finally, high-performance liquid chromatography data appear to indicate that radiosterilization of captopril is feasible.

Comparative X- and Q-band EPR study of radiation-induced radicals in tooth enamel.

Human tooth enamel blocks and powders that were either unheated or heated prior to X irradiation at room temperature were investigated by means of Q-band electron paramagnetic resonance (EPR). It was found that the EPR spectra of unheated human tooth enamel consist mainly of two different anisotropic signals, as was suggested previously from an X-band study of analogous samples. In the present study, the two radical contributions could be differentiated convincingly by comparing the anisotropic Q-band spectra of heated and unheated enamel blocks. One type of is probably located in the bulk of the apatitic microcrystallites that constitute the enamel, and it appears in both heated and unheated samples. The other type is presumably located in an intercrystallite position and appears mainly in the unheated samples. Clear differences between g values in the Q-band spectra of heated and unheated enamel suggest that the radicals in the bulk exhibit larger g anisotropy than those in intercrystallite positions. Isotropic signals and contributions that may be from and radicals have also been detected. However, the present work focuses mainly on the signals and discusses potential and/or real difficulties that may be encountered in applications of EPR dosimetry using calcified tissues.