Nadica Maltar-Strmečki

Relaxation mechanism in γ-ray-irradiated L-alanine studied by transfer saturation EPR and pulse EPR

Stable paramagnetic centers in γ-ray-irradiated L-alanine dosimeters exhibit a maximum in relaxation rate in the vicinity of 190 K. The mechanism of this relaxation rate has been investigated on the first stable alanine radical center, SARI, by employing continuous-wave transfer saturation electron paramagnetic resonance and pulse electron paramagnetic resonance techniques. The detected in-phase and out-of-phase spectra as well as phase memory times,TM, indicate that besides the well-known τp of the CH3 group of SAR1 an additional correlation time, τl (ΔElk=2689±50 K and 0 τ10 = 0.15 ± 0.03 ps), is involved in the transverse relaxation process and effects the SAR1 center. For the SAR1 center this mechanism originates from the hindered motion of undamaged CH3 and NH3+ groups in the lattice. The motion of these groups additionally effects the spectrum of the SAR1 center through averaging out of the anisotropic splitting.

Study of relaxation rates of stable paramagnetic centers in γ-irradiated alanine

The stable L-alanine radical induced by gamma-irradiation was examined by electron paramagnetic resonance (EPR), transfer saturation EPR and electron nuclear double resonance (ENDOR) in the temperature region of fast motion of the methyl group (180-320 K). From the obtained spectral line broadening and spectral intensity the correlation time for the methyl rotation was estimated. The complex processes determining the relaxation rate were examined in the same temperature interval. It was shown that important contributions to the relaxation rate arise from non-secular and pseudo-secular types of contributions. The non-secular contribution involves intramolecular dynamics while the pseudo-secular contribution originates from intermolecular motions. The obtained values for the dynamical parameters have been compared with those obtained by pulse EPR methods and by proton nuclear magnetic resonance (NMR) on undamaged crystals.

ENDOR study of the dynamic properties of stable paramagnetic centres in γ -irradiated L-alanine crystals

The dynamic properties of the stable L-alanine radicals SAR1 and SAR2 induced by γ-irradiation of a L-alanine crystal have been investigated using the electron nuclear double resonance technique (ENDOR). The study was focused on the dynamic properties of these centres in the temperature range from 180 to 320 K. In this region, the motion of the and CH3 groups exhibits slow and fast motional dynamics in comparison with the nuclear and electron Larmor frequencies, respectively. The correlation rotation times of the CH3 and groups of the SAR2 CH3 group and the neighbouring CH3 group of the SAR1 paramagnetic centre were estimated from the spectral line broadening and spectral intensity.

Investigation of the nitrogen hyperfine coupling of the second stable radical in γ-irradiated l-alanine crystals by 2D-HYSCORE spectroscopy.

The second stable radical, NH(3)(+)C()(CH(3))COO(-), R2, in the γ-irradiated single crystal of l-alanine and its fully (15)N-enriched analogue were studied by an advanced pulsed EPR technique, 2D-HYSCORE (two-dimensional hyperfine sublevel correlation) spectroscopy at 200K. The nitrogen hyperfine coupling tensor of the R2 radical was determined from the HYSCORE data and provides new experimental data for improved characterization of the R2 radical in the crystal lattice. The results obtained complement the experimental proton data available for the R2 radical and could lead to increased accuracy and reliability of EPR spectrum simulations.

How similar are amorphous calcium carbonate and calcium phosphate? A comparative study of amorphous phase formation conditions

Amorphous calcium carbonate (ACC) and calcium phosphate (ACP) increasingly attract attention as initial solid phases in vertebrate and invertebrate hard tissue formation, as well as in materials science as a possible new synthetic route for advanced materials preparation. Although much is known about these two amorphous phases and similarities in the mechanisms of their formation are recognized, no attempt has been made to investigate their formation under defined and comparable initial experimental conditions viz supersaturation, constituent ions ratio, ionic strength and presence of relevant inorganic additives. In this paper, the formation of ACC and ACP in three model precipitation systems of increased chemical complexity were investigated: (a) systems containing constituent ions, (b) systems containing additional co-ions, and (c) systems with higher ionic strength and addition of Mg2+. The results have shown that ACP is more stable and was formed at lower relative supersaturations in comparison to ACC. The precipitation domain of both phases expanded with increasing complexity of precipitation systems, with the ACP precipitation domains always being larger than that of ACC. In addition to stability, the presence of inorganic ions, especially Mg2+, influences the composition of both amorphous phases. The obtained results indicate that general similarity between ACC and ACP exists, but it could also be concluded that similar chemical environment in which they form not necessary lead to similar structural properties.

The effect of thermal treatment of radiation-induced EPR signals of different polymorphic forms of trehalose.

Electron paramagnetic resonance (EPR) signals induced by γ-radiation in different polymorphic forms of trehalose were studied with dosimetry applications in view. Dose response of trehalose in terms of the concentration of induced paramagnetic centers was studied in the dose range from 0.5 to 50 kGy. The dependences of the dose responses of anhydrous β-crystalline trehalose (TRE(β)) and glassy trehalose (TRE(g)) on dose are linear up to 15 kGy, whereas the linearity of the dependence for trehalose dihydrate (TRE(h)) is limited to about 10 kGy. At doses above 15 kGy, the dependences get saturated for all three forms. The relative radiation sensitivities pointed to the following order of decreasing concentrations of radiation-induced paramagnetic centers in the forms: TRE(g)>TRE(β)>TRE(h). The results showed that at all three trehalose polymorphic forms are suitable for dosimetry, especially for retrospective dose measurements. Also, thermal stability and decay kinetics of the EPR signals of the different forms of trehalose were studied in isothermal annealing experiments. The kinetic parameters, which had been derived by fitting the Arrhenius function to the measured decay rate constants, indicated that the fading of the EPR signals varied from one polymorphic form of trehalose to another. This emphasizes the impact of the molecular packing in the vicinity of the radiation-induced paramagnetic centers on their stability.

ENDOR Study on the Dynamic Properties of the First Stable Paramagnetic Center in γ-Irradiated L-Alanine Crystals

Dynamic properties of the first stable l-alanine radical, SAR1, induced by gamma-irradiation of l-alanine crystals, have been investigated by the electron nuclear double resonance technique (ENDOR). The study focuses on the dynamic properties of the alpha-proton hyperfine splitting in the temperature range from 180 to 320 K. In this region the motion of the NH(3)(+) and CH(3) groups exhibits slow and fast motional dynamics in comparison to the nuclear and electron Larmor frequencies, respectively. Evidence for different conformations of the SAR1 center is presented on the basis of thermodynamic properties of the alpha-hyperfine splitting. The activation processes causing the broadening of the ENDOR lines are studied. At room temperature the motional dynamics of the SAR1 center are modulated by the dynamics of the charged, neighboring NH(3)(+) group.