Synthesis, Characterization and Assessment of the Antioxidant Activity of Cu(II), Zn(II) and Cd(II) Complexes Derived from Scorpionate Ligands.

Seeking to enrich the yet less explored field of scorpionate complexes bearing antioxidant properties, we, here, report on the synthesis, characterization and assessment of the antioxidant activity of new complexes derived from three scorpionate ligands. The interaction between the scorpionate ligands thallium(I) hydrotris(5-methyl-indazolyl)borate (TlTp4Bo,5Me), thallium(I) hydrotris(4,5-dihydro-2H-benzo[g]indazolyl)borate (TlTpa) and potassium hydrotris(3-tert-butyl- pyrazolyl)borate (KTptBu), and metal(II) chlorides, in dichloromethane at room temperature, produced a new family of complexes having the stoichiometric formula [M(Tp4Bo,5Me)2] (M = Cu, 1; Zn, 4; Cd, 7), [M(Tpa)2] (M = Cu, 2; Zn, 5; Cd, 8), [Cu(HpztBu)3Cl2] (3), [Zn(TptBu)Cl] (6) and [Cd(BptBu)(HpztBu)Cl] (9). The obtained metal complexes were characterized by Fourier transform infrared spectroscopy, proton nuclear magnetic resonance and elemental analysis, highlighting the total and partial hydrolysis of the scorpionate ligand TptBu during the synthesis of the Cu(II) complex 3 and the Cd(II) complex 9, respectively. An assessment of the antioxidant activity of the obtained metal complexes was performed through both enzymatic and non-enzymatic assays against 1,1-diphenyl-2-picryl- hydrazyl (DPPH·), 2,2'-Azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS+·), hydroxyl (HO·), nitric oxide (NO·), superoxide (O2-) and peroxide (OOH·) radicals. In particular, the complex [Cu(Tpa)2]⋅0.5H2O (2) exhibited significant antioxidant activity, as good and specific activity against superoxide (O2-·), (IC50 values equal to 5.6 ± 0.2 µM) and might be identified as auspicious SOD-mimics (SOD = superoxide dismutase).

The Effects of Radiation and Emitted Light Transport on the Positional Response of 11 cm × 42.5 cm × 5.5 cm NaI(Tl) Detectors.

Experiments were performed with 30 11 cm × 42.5 cm × 5.5 cm NaI(Tl) detectors to better understand their positional response. Spectra were collected using 0.02 to 0.15 MBq point sources of Am, Cs, Co, and Ba positioned on lines parallel and perpendicular to the long axis of the crystal along both the narrow and wide detector faces as well as at different distances from them. A greater density of positions was sampled at the ends of the detector, and repeated measurements were made to examine potential gain drifts during the experiment. Spectroscopic peak counts, spectroscopic pulse heights, and net counts were analyzed. Empirical equations were fit to the aforementioned data for each specific source energy as a function of source position. In addition, a Monte Carlo radiation transport code was used to simulate the expected positionally variable response based solely upon radiation absorption. The simulated radiation transport efficiency functions were compared to the experimental data. The effects of the geometric radiation efficiency, the attenuation and scattering of emitted light within the scintillation crystal, and combined effects such as nonuniformity of the photomultiplier tube, photocathode response, and crystal irregularities were then distinguished. Functions describing each effect were derived. The results suggest potential new corrections to data obtained with large scintillation detectors as well as a novel approach to partial positional gamma-ray detection with minimal collimation, given that the energy resolution is within reason for particular photopeaks.

MCNP SIMULATIONS WITH A PERSONALISED VOXEL PHANTOM TO VERIFY 131I CONTENT IN THYROID ESTIMATED BASED ON MEASUREMENTS WITH AN NaI(Tl) SPECTROMETER.

One of the authors (O.K.) stayed in the area located ~110 km south from the Fukushima Daiichi Nuclear Power Plant during the arrival of radioactive plumes released into the environment due to the accident in March 2011 in Japan. A previous study determined his 131I thyroid content using an NaI(Tl) spectrometer. The one remaining issue was to investigate the measurement error due to inevitable differences in the configuration (e.g. the thyroid shape and volume) between the physical phantom employed for calibration of the spectrometer and the real subject. In the present study, Monte Carlo simulations for the thyroid measurements were performed using the Monte Carlo N-Particle (MNCP) code to investigate discrepancies in peak efficiencies of the spectrometer between the personalised voxel phantom created from O.K.'s magnetic resonance images and the several typical/reference phantoms that exist. As a result, the peak efficiencies for the Oak Ridge Institute of Nuclear Studies (ORINS) phantom were found to be comparable to those for the reference voxel phantoms reproducing realistic human anatomy (the Adult Male phantom and the Japanese Male phantom). The peak efficiency for the personalised phantom, on the other hand, was fairly close to that of the other physical phantom (the Transfer phantom) actually used for the calibration of the spectrometer, suggesting that the 131I thyroid content determined for him in the previous study was sufficiently accurate. The discrepancies of peak efficiencies at the primal photon energy of 131I (365 keV) among the different phantoms were improved by extending the distance between the neck and the spectrometer; however, the appropriate measurement geometry in an actual situation will depend on the primary purpose of the measurements and should be determined accordingly.

Monte Carlo simulation of NaI(TL) detector in a shadow-shield scanning bed whole-body monitor for uniform and axial cavity activity distribution in a BOMAB phantom.

This study presents the simulation results for 10.16 cm diameter and 7.62 cm thickness NaI(Tl) detector response, which is housed in a partially shielded scanning bed whole-body monitor (WBM), due to activity distributed in the axial cavities provided in the Indian reference BOMAB phantom. Experimental detection efficiency (DE) for axial cavity activity distribution (ACAD) in this phantom for photon emissions of (133)Ba, (137)Cs and (60)Co is used to validate DEs estimated using Monte Carlo code FLUKA. Simulations are also carried out to estimate DEs due to uniform activity distribution (UAD) as in the standard BOMAB phantom. The results show that the DE is ∼3.8 % higher for UAD when compared with ACAD in the case of (40)K (1460 keV) and this relative difference increases to ∼7.0 % for (133)Ba (∼356 keV) photons. The corresponding correction factors for calibration with Indian phantom are provided. DEs are also simulated for activity distributed as a planar disc at the centre of the axial cavity in each part of the BOMAB phantom (PDAD) and the deviations of these DEs are within 1 % of the ACAD results. Thus, PDAD can also be used for ACAD in scanning geometry. An analytical solution for transmitted mono-energetic photons from a two-dimensional slab is provided for qualitative explanation of difference in DEs due to variation in activity distributions in the phantom. The effect on DEs due to different phantom part dimensions is also studied and lower DEs are observed for larger parts.

A Monte Carlo evaluation of three Compton camera absorbers.

We present a quantitative study on the performance of cadmium zinc telluride (CZT), thallium-doped sodium iodide (NaI(Tl)) and germanium (Ge) detectors as potential Compton camera absorbers. The GEANT4 toolkit was used to model the performance of these materials over the nuclear medicine energy range. CZT and Ge demonstrate the highest and lowest efficiencies respectively. Although the best spatial resolution was attained for Ge, its lowest ratio of single photoelectric to multiple interactions suggests that it is most prone to inter-pixel cross-talk. In contrast, CZT, which demonstrates the least positioning error due to multiple interactions, has a comparable spatial resolution with Ge. Therefore, we modelled a Compton camera system based on silicon (Si) and CZT as the scatterer and absorber respectively. The effects of the detector parameters of our proposed system on image resolution were evaluated and our results show good agreement with previous studies. Interestingly, spatial resolution which accounted for the least image degradation at 140.5 keV became the dominant degrading factor at 511 keV, indicating that the absorber parameters play some key roles at higher energies. The results of this study have validated the predictions by An et al. which state that the use of a higher energy gamma source together with reduction of the absorber segmentation to sub-millimetre could achieve the image resolution of 5 mm required in medical imaging.

Accurate Monte Carlo modelling of the back compartments of SPECT cameras.

Today, new single photon emission computed tomography (SPECT) reconstruction techniques rely on accurate Monte Carlo (MC) simulations to optimize reconstructed images. However, existing MC scintillation camera models which usually include an accurate description of the collimator and crystal, lack correct implementation of the gamma camera's back compartments. In the case of dual isotope simultaneous acquisition (DISA), where backscattered photons from the highest energy isotope are detected in the imaging energy window of the second isotope, this approximation may induce simulation errors. Here, we investigate the influence of backscatter compartment modelling on the simulation accuracy of high-energy isotopes. Three models of a scintillation camera were simulated: a simple model (SM), composed only of a collimator and a NaI(Tl) crystal; an intermediate model (IM), adding a simplified description of the backscatter compartments to the previous model and a complete model (CM), accurately simulating the materials and geometries of the camera. The camera models were evaluated with point sources ((67)Ga, (99m)Tc, (111)In, (123)I, (131)I and (18)F) in air without a collimator, in air with a collimator and in water with a collimator. In the latter case, sensitivities and point-spread functions (PSFs) simulated in the photopeak window with the IM and CM are close to the measured values (error below 10.5%). In the backscatter energy window, however, the IM and CM overestimate the FWHM of the detected PSF by 52% and 23%, respectively, while the SM underestimates it by 34%. The backscatter peak fluence is also overestimated by 20% and 10% with the IM and CM, respectively, whereas it is underestimated by 60% with the SM. The results show that an accurate description of the backscatter compartments is required for SPECT simulations of high-energy isotopes (above 300 keV) when the backscatter energy window is of interest.

Thallium dynamics in contrasting light sandy soils--soil vulnerability assessment to anthropogenic contamination.

The influence of different soil conditions and the presence of LMWOA (Low Molecular Weight Organic Acids) on anthropogenic Tl dynamics were discussed in this study. A shift from the "labile" to the residual fraction during the ageing was identified, indicating Tl incorporation into stable phases (e.g., illite and/or amorphous silicates). The increased water-soluble Tl concentration (1.8-fold, in maximum) after the split application of LMWOA (simulating root exudation) was observed in all soils; partial dissolution of relatively "insoluble" Tl-bearing phases (silicates and eventually oxides) in the presence of LMWOA is suggested. Thermodynamic modeling showed that Tl mobilization in the presence of citric and oxalic acids was indirect and could be attributed to complexation of major elements (Ca, Mg, Al) originating from the dissolution of various soil phases. On the contrary, H(+)-promoted dissolution by acetic acid was assumed as the predominant mechanism of Tl mobilization. Manganese(III,IV) oxides, illite and probably amorphous silicates were evaluated as the dominant phases responsible for Tl retention in the soils. In carbonate-rich soils, Tl coprecipitation with the newly formed carbonates seems to be an important factor influencing Tl release. Therefore, we suggest data on CEC, pH(ZPC) and soil mineralogy to be critical for assessment of Tl behavior in soil systems.

Assessment of extractants for the determination of thallium in an accidentally polluted soil.

Thallium is a rare and easily dispersed element with high toxicity to organisms. Relatively high levels of thallium (approximately 9.58 mg kg(-1)) had been found in aqua regia soil extract of an accidentally polluted soil from south of Spain. To assess the available and leachable portions of thallium in the polluted soil, single and sequential extraction procedures have been utilized. Further, X-ray diffraction and scanning electron microscopic studies have also been used to find out the mineral phases. The amount of thallium extracted by the extracting agents in comparison to aqua regia, as well as the different phase associations are discussed.

Tl+-induced micros gating of current indicates instability of the MaxiK selectivity filter as caused by ion/pore interaction.

Patch clamp experiments on single MaxiK channels expressed in HEK293 cells were performed at high temporal resolution (50-kHz filter) in asymmetrical solutions containing 0, 25, 50, or 150 mM Tl+ on the luminal or cytosolic side with [K+] + [Tl+] = 150 mM and 150 mM K+ on the other side. Outward current in the presence of cytosolic Tl+ did not show fast gating behavior that was significantly different from that in the absence of Tl+. With luminal Tl+ and at membrane potentials more negative than -40 mV, the single-channel current showed a negative slope resistance concomitantly with a flickery block, resulting in an artificially reduced apparent single-channel current I(app). The analysis of the amplitude histograms by beta distributions enabled the estimation of the true single-channel current and the determination of the rate constants of a simple two-state O-C Markov model for the gating in the bursts. The voltage dependence of the gating ratio R = I(true)/I(app) = (k(CO) + k(OC))/k(CO) could be described by exponential functions with different characteristic voltages above or below 50 mM Tl(+). The true single-channel current I(true) decreased with Tl+ concentrations up to 50 mM and stayed constant thereafter. Different models were considered. The most likely ones related the exponential increase of the gating ratio to ion depletion at the luminal side of the selectivity filter, whereas the influence of [Tl+] on the characteristic voltage of these exponential functions and of the value of I(true) were determined by [Tl+] at the inner side of the selectivity filter or in the cavity.

Analysis and improvement of cyclotron thallium target room shield.

Because of high neutron and gamma-ray intensities generated during bombardment of a thallium-203 target, a thallium target-room shield and different ways of improving it have been investigated. Leakage of neutron and gamma ray dose rates at various points behind the shield are calculated by simulating the transport of neutrons and photons using the Monte Carlo N Particle transport computer code. By considering target-room geometry, its associated shield and neutron and gamma ray source strengths and spectra, three designs for enhancing shield performance have been analysed: a shielding door at the maze entrance, covering maze walls with layers of some effective materials and adding a shadow-shield in the target room in front of the radiation source. Dose calculations were carried out separately for different materials and dimensions for all the shielding scenarios considered. The shadow-shield has been demonstrated to be one suitable for neutron and gamma dose equivalent reduction. A 7.5-cm thick polyethylene shadow-shield reduces both dose equivalent rate at maze entrance door and leakage from the shield by a factor of 3.

Calculation of total counting efficiency of a NaI(Tl) detector by hybrid Monte-Carlo method for point and disk sources.

This paper presents results on the total gamma counting efficiency of a NaI(Tl) detector from point and disk sources. The directions of photons emitted from the source were determined by Monte-Carlo techniques and the photon path lengths in the detector were determined by analytic equations depending on photon directions. This is called the hybrid Monte-Carlo method where analytical expressions are incorporated into the Monte-Carlo simulations. A major advantage of this technique is the short computation time compared to other techniques on similar computational platforms. Another advantage is the flexibility for inputting detector-related parameters (such as source-detector distance, detector radius, source radius, detector linear attenuation coefficient) into the algorithm developed, thus making it an easy and flexible method to apply to other detector systems and configurations. The results of the total counting efficiency model put forward for point and disc sources were compared with the previous work reported in the literature.