Preparation and comparative structural properties of porous SnO2 microrods and submicrorods

A facile two-step approach has been used for the synthesis of porous SnO₂ rods: the initial room-temperature precipitation of precursor SnC₂O₄ and its subsequent thermal decomposition at 550 °C. Both the as-obtained porous SnO₂ microrods (length ～10.0?±?3.5 μm, diameter ～1.1?±?0.4 μm) and submicrorods (length ～5.8?±?1.9 μm, diameter ～0.4?±?0.1 μm) are the crystalline mixtures of major tetragonal and minor orthorhombic crystal phases, showing a tetragonal fraction of 84.7 and 87.0 %, respectively. When applied as a lithium-ion battery anode, the porous submicrorods (specific surface area ～13.6 m² g^?1) can deliver an initial discharge capacity of 1,730.7 mAh g^?1 with a high coulombic efficiency of 61.6 % and show the 50th discharge capacity of 662.8 mAh g^?1 at 160 mA g^?1 within a narrow potential range of 10.0 mV to 2.0 V. Similarly, even the anode of porous microrods (specific surface area ～11.8 m² g^?1) can still exhibit an initial discharge capacity of 1,661.1 mAh g^?1 at 160 mA g^?1 with a coulombic efficiency of 60.9 %. Regardless of the polymorphic nature, the acquired porosity may only alleviate the huge volume change of anodes for the first cycle; thus, the structural parameters of average size and specific surface area can be feasibly associated with the enhanced lithium storage capability. Anyway, these indicate a facile oxalate precursor method for the controlling synthesis and high performance of rodlike SnO₂ for lithium-ion batteries.     

Single-crystal elasticity of the rhodochrosite at high pressure by Brillouin scattering spectroscopy

ABSTRACT

The sound velocity properties of single-crystal rhodochrosite (MnCO₃) were determined up to 9.7?GPa at ambient temperature by Brillouin scattering spectroscopy. Six elastic constants were calculated by a genetic algorithm method using the Christoffel's equations at each pressure. The elastic constants increased linearly as a function of pressure and its pressure derivatives ?Cij/?P for C₁₁, C₃₃, C₄₄, C₁₂, C₁₃, C₁₄ were 5.86 (±0.36), 3.82 (±0.44), 2.06 (±0.39), 5.07 (±0.27), 5.34 (±0.44), 1.52 (±0.24), respectively. Based on the derived elastic constants of rhodochrosite, the aggregate adiabatic bulk and shear moduli (K_s and G) were calculated using the Voigt-Reuss-Hill averages and the linear fitting coefficients (?K_s/?P)_T and (?G/?P)_T were 5.05(±0.26) and 0.73(±0.05), respectively. The aggregate V_p of rhodochrosite increased clearly as a function of pressure and its pressure derivative ?V_p/?P was 7.99(±0.53)?×?10^?2?km/(s?GPa), while the aggregate V_s increased slowly and ?V_s/?P was only 1.19(±0.12)?×?10^?2?km/(s?GPa). The anisotropy factor for As of rhodochrosite increased from ～40% at 0.8?GPa to ～48% at 9.7?GPa, while A_p decreased from ～19% to ～16% at the corresponding pressure.     

Activity concentrations of 226Ra, 232Th, 40K and 137Cs radionuclides in Turkish medicinal herbs,their ingestion doses and cancer risks

Twenty-two medicinal herb samples, each representing a distinct species, were collected from Turkish markets and measured by the gamma spectrometric method. The activity concentration of ²²⁶Ra in medicinal herbs was found in the range of minimum detectable activity (MDA) and 15.1?±?2.2?Bqkg^?1. The activity concentration of ²³²Th ranged from MDA values to 3.5?±?0.8?Bqkg^?1. The activity concentration of ⁴⁰K varied between 50.0?±?16.8 and 1311.5?±?57.3?Bqkg^?1. All ¹³⁷Cs activity concentrations of medicinal herbs were found to have lower than MDA values. The bone surface dose, lower large intestine and colon doses were found to be 182.9, 18.8 and 18.7?µSvy^?1, respectively. The highest committed effective dose originated from the annual ingestion of 1?kg medicinal herb was calculated notably low as 9.0?µSv. The cancer risk of ingestion of medicinal herbs was found to be small enough to be neglected. The selected Turkish medicinal herbs are considered safe for human consumption.     

The Massachusetts Toxics Use Reduction Act: a model for nanomaterials regulation?

Polyvinylimidazole (PVIm)-grafted superparamagnetic iron oxide nanoparticles (SPION) (Si-PVIm-grafted Fe₃O₄ NPs) were prepared by grafting of telomere of PVIm on the SPION. The product identified as magnetite, which has an average crystallite size of 9?±?2?nm as estimated from X-ray line profile fitting. Particle size was estimated as 10.0?±?0.5?nm from TEM micrographs. Mean particle size is found as 8.4?±?1.0?nm which agrees well with the values calculated from XRD patterns (9?±?2?nm). Vibrating Sample Magnetometer (VSM) analysis explained the superparamagnetic nature of the nanocomposite. Thermogravimetric analysis showed that the Si-Imi is 25?% of the Si-PVIm-grafted SPION, which means an inorganic content is about 75?%. Detailed electrical and dielectric properties of the properties of the product are also presented. The conductivity of the sample increases significantly with temperature and has the value in the range of 1.14?×?10^?7?C1.78?×?10^?4?S?cm^?1. Analysis of the real and imaginary parts of the permittivities indicated temperature and frequency dependency representing interfacial polarization and temperature-assisted reorganization effects.     

Natural radioactivity and radiation hazards assessment of soil samples from the area of Tuzla and Lukavac,Bosnia and Herzegovina

The results of activity concentration measurements of natural occurring radioactive nuclides ²³⁸U, ²³⁵U, ²³²Th, ²²⁶Ra, and ⁴⁰K in surface soil samples collected in the area of cities Tuzla and Lukavac, northeast region of Bosnia and Herzegovina were presented. Soil sampling was conducted at the localities that are situated in the vicinity of industrial zones of these cities. The measured activity was in the range from (8?±?4) to (95?±?28) Bq kg^–1 for ²³⁸U, from (0.41?±?0.06) to (4.6?±?0.7) Bq kg^–1 for ²³⁵U, from (7?±?1) to (66?±?7) Bq kg^–1 for ²³²Th, from (6?±?1) to (55?±?6) Bq kg^–1 for ²²⁶Ra, and from (83?±?12) to (546?±?55) Bq kg^–1 for ⁴⁰K. In order to evaluate the radiological hazard of the natural radioactivity for people living near industrial zones, the absorbed dose rate, the annual effective dose and the radium equivalent activity have been calculated and compared with the internationally approved values.     

Unexpected radiation hazard in dyes of textiles

Textile dyes are among the most problematic pollutants because of their toxicity on several organisms and ecosystems. Many of the chemicals used in the textile industry may represent some health concerns. The determination of the radioactivity in textile dyes is therefore very important for both human health and environment. The study was designated to determine, for the first time, the values of ²³⁸U, ²³²Th and ⁴⁰K in nine different dyes employed in the textile industry using gamma spectrometry with a Hyper Pure Germanium (HPGe) detector. The mean activity concentrations of ²³⁸U, ²³²Th and ⁴⁰K were 29.37?±?4.48, 1.15?±?0.13 and 565?±?4 Bq/kg, respectively. The calculated radium equivalents for all samples were lower than the maximum admissible value (370 Bq/kg). The absorbed dose rates due to the natural radioactivity of the investigated samples ranged from 2.94?±?0.05 to 166?±?3 nGy/h. So, the absorbed dose rates for all samples of textile dyes were lower than the international recommended value (55 nGy/h) except the yellow dye (166?±?3 nGy/h), which recorded a significant radiological hazard. The external hazard index was also calculated. Conclusively, the results have indicated that the textile dyes may possess a measurable amount of radioactivity that should be taken into account. Therefore, safety rules and precautions should be applied for dyes used in the textile industry and for people working in this field.     

The determination of concentrations of radioisotopes in some granite samples in Turkey and their radiation hazards

The primordial radionuclides activity concentrations (²²⁶Ra, ⁴⁰K and ²³²Th) are measured in some granite samples in this study. The collected granite materials are analyzed with NaI(Tl) gamma-ray spectrometry. The specific activity of ²²⁶Ra, ²³²Th and ⁴⁰K values are in range 2.60?±?0.10 to 178.9?±?0.6?Bq?kg^?1, 1.46?±?0.10 to 162.50?±?0.75?Bq?kg^?1 and 19.8?±?0.3 to 579.7?±?2.8?Bq?kg^?1 respectively. The radium’s equivalent activity, annual effective dose, absorbed dose rate, hazard index, radioactivity level index, activity utilization’s index and exposure rate are calculated for determination of radiological risk. The concentration of ²²⁶Ra (in the 71.4% of samples), ²³²Th (in the 71.4% of samples) and ⁴⁰K (in the 14.3% of samples) in the granite samples are higher than average radioactivity concentrations of this radio-isotopes defined by ICRP (35.0, 30.0 and 400.0?Bq?kg^?1, respectively).     

Kinetics of the gas‐phase homogeneous unimolecular elimination of selected ethyl esters of 2‐oxo‐carboxylic acids

The gas‐phase elimination kinetics of selected ethyl esters of 2‐oxo‐carboxylic acid have been studied over the temperature range of 270–415 °C and pressures of 37–114 Torr. The reactions are homogeneous, unimolecular, and follow a first‐order rate law in a seasoned static reaction vessel, with an added free radical suppressor toluene. The observed overall and partial rate coefficients are expressed by the following Arrhenius equations:

• Ethyl oxalyl chloride
• log k_overall (s^?1) = (13.22 ± 0.45) ? (179.4 ± 4.9) kJ mol^?1 (2.303 RT)^?1
• Ethyl piperidineglyoxylate
• log k_(CO2) (s^?1) = (12.00 ± 0.30) ? (191.2 ± 3.9) kJ mol^?1 (2.303 RT)^?1
• log k_(CO) (s^?1) = (12.60 ± 0.09) ? (210.7 ± 1.2) kJ mol^?1 (2.303 RT)^?1
• log k_t(overall) (s^?1) = (12.22 ± 0.26) ? (193.4 ± 3.4) kJ mol^?1 (2.303 RT)^?1
• Ethyl benzoyl formate
• log k_(CO2) (s^?1) = (12.89 ± 0.72) ? (203.8 ± 9.0) kJ mol^?1 (2.303 RT)^?1
• log k_(CO) (s^?1) = (13.39 ± 0.31) ? (213.3 ± 3.9) kJ mol^?1 (2.303 RT)^?1
• log k_t(overall) (s^?1) = (13.24 ± 0.60) ? (205.8 ± 7.6) kJ mol^?1 (2.303 RT)^?1

The kinetic and thermodynamic parameters of these reactions, together with those reported in the literature, lead to consider three different mechanistic pathways of elimination. Copyright © 2010 John Wiley & Sons, Ltd.     

Natural radioactivity measurements in Pahang State,Malaysia

This study was aimed at providing the baseline data of terrestrial gamma dose rates and natural radioactivity to assess the corresponding health risk in the ambient environment of the Pahang State. Terrestrial gamma radiation (TGR) from 640 locations was measured with the mean value found to be 176?±?5 nGy h^?1. Ninety-eight soil samples were analysed using a high-purity germanium detector (HPGe), and the mean concentrations of the radionuclides ²²⁶Ra, ²³²Th and ⁴⁰K are 110?±?3, 151?±?5 and 542?±?51 Bq kg^?1, respectively.²²⁶Ra and ²³²Th concentrations were found to be three times the world average, while that of ⁴⁰K is quite higher than the world average value. The acid-intrusive geological formation has the highest mean concentrations for ²²⁶Ra (215?±?6 Bq kg^?1), ²³²Th (384?±?12 Bq kg^?1) and ⁴⁰K (1564?±?153 Bq kg^?1). The radium equivalent activities (Req) and the external hazard index (Hex) for the various soil types were also calculated. Some of the soil types were found to have values exceeding the internationally recommended levels of 370 Bq kg^?1 and the unity value, respectively.     

Simultaneous measurements of indoor radon and thoron and inhalation dose assessment in Douala City,Cameroon

ABSTRACT

Radon, thoron and associated progeny measurements have been carried out in 71 dwellings of Douala city, Cameroon. The radon–thoron discriminative detectors (RADUET) were used to estimate the radon and thoron concentration, while thoron progeny monitors measured equilibrium equivalent thoron concentration (EETC). Radon, thoron and thoron progeny concentrations vary from 31?±?1 to 436?±?12 Bq?m^–3, 4?±?7 to 246?±?5 Bq?m^–3, and 1.5?±?0.9 to 13.1?±?9.4 Bq?m^–3. The mean value of the equilibrium factor for thoron is estimated at 0.11?±?0.16. The annual effective dose due to exposure to indoor radon and progeny ranges from 0.6 to 9?mSv?a^–1 with an average value of 2.6?±?0.1?mSv?a^–1. The effective dose due to the exposure to thoron and progeny vary from 0.3 to 2.9?mSv?a^–1 with an average value of 1.0?±?0.4?mSv?a^–1. The contribution of thoron and its progeny to the total inhalation dose ranges from 7 to 60?% with an average value of 26?%; thus their contributions should not be neglected in the inhalation dose assessment.     

The keto-enol equilibrium in substituted acetaldehydes: focal-point analysis and ab initio limit

High-level ab initio electronic structure calculations up to the CCSD(T) theory level, including extrapolations to the complete basis set (CBS) limit, resulted in high precision energetics of the tautomeric equilibrium in 2-substituted acetaldehydes (XH₂C-CHO). The CCSD(T)/CBS relative energies of the tautomers were estimated using CCSD(T)/aug-cc-pVTZ, MP3/aug-cc-pVQZ, and MP2/aug-cc-pV5Z calculations with MP2/aug-cc-pVTZ geometries. The relative enol (XHC?=?CHOH) stabilities (ΔE _{e,CCSD(T)/CBS}) were found to be 5.98?±?0.17, ?1.67?±?0.82, 7.64?±?0.21, 8.39?±?0.31, 2.82?±?0.52, 10.27?±?0.39, 9.12?±?0.18, 5.47?±?0.53, 7.50?±?0.43, 10.12?±?0.51, 8.49?±?0.33, and 6.19?±?0.18?kcal?mol^?1 for X?=?BeH, BH₂, CH₃, Cl, CN, F, H, NC, NH₂, OCH₃, OH, and SH, respectively. Inconsistencies between the results of complex/composite energy computations methods Gn/CBS (G2, G3, CBS-4M, and CBS-QB3) and high-level ab initio methods (CCSD(T)/CBS and MP2/CBS) were found. DFT/aug-cc-pVTZ results with B3LYP, PBE0 (PBE1PBE), TPSS, and BMK density functionals were close to the CCSD(T)/CBS levels (MAD?=?1.04?kcal?mol^?1).     

Thermochemical properties of small open-shell systems: experimental and high-level ab initio results for NH2 and

The first adiabatic ionization energy and the first singlet–triplet splitting of the amidogen radical (NH₂) have been determined by high-level ab initio quantum chemistry based on the coupled-cluster approach (90?041 and 10?319?cm^?1, respectively) and by high-resolution pulsed-field-ionization zero-kinetic-energy (PFI-ZEKE) photoelectron spectroscopy (90 083.8 ± 1.0 and 10 222.0 ± 1.3?cm^?1, respectively). A comparison between the theoretical and experimental values demonstrates the predictive powers of high-level ab initio theory in the derivation of the thermochemical properties of small molecular systems. The absolute accuracy of better than 100?cm^?1 alleviates the experimental search for the relevant spectral features.     

ESR and optical study of Cu2+-doped bis-(5,5′-diethylbarbiturato)bis picoline Zn(II)

ESR studies were conducted on Cu²⁺-doped bis-(5,5′-diethylbarbiturato)bis picoline Zn(II). Two Cu²⁺ lattice sites, Cu²⁺(I) and Cu²⁺(II), were identified. These sites exhibit two sets of four hyperfine lines in all directions. The g factor and hyperfine splitting were calculated from ESR absorption spectra: g_x ?=?2.0201?±?0.002, g_y ?=?2.0900?±?0.002, g_z ?=?2.1634?±?0.002, A_x ?=?(30?±?2)?×?10^?4?cm^?1, A_y ?=?(40?±?2)?×?10^?4?cm^?1 and A_z ?=?(154?±?2)?×?10^?4?cm^?1. It was found that Cu²⁺ enters the lattice substitutionally. The ground-state wavefunction of the Cu²⁺ ion in this lattice was determined from the spin Hamiltonian constants obtained from the ESR studies. With the help of an optical absorption study, the nature of the bonding in the complex is also discussed.     

Inclusive production of non-strange resonances inK − p interactions at 32 GeV/c

New data on the inclusive production of the non-strange resonances ?⁰(770), ω(783), ?(1020) andf(1270) inK ^? p interactions at 32 GeV/c are presented. The inclusive production cross sections are equal to (4.32±0.72) mb, (3.7±1.4) mb, (0.65±0.10) mb and (0.91±0.35) mb respectively. Estimates of the topological cross sections are also obtained. The invariant and non-invariantx-distributions for the vector mesons ?⁰ and ? indicate the prevalence of forward resonance production in the c.m. system. For the tensorf-meson the rapidity andx-distributions are presented. Thet′-distributions for ?⁰, ?, andf have exponential slopes of 0.6±0.1 GeV^?2, 1.2±0.2 GeV^?2, and 0.8±0.5 GeV^?2 respectively. The exponential slope ofp _T ² -distribution of thef-meson is equal to (2.3±0.5) GeV^?2.     

The relative isotopic abundance (δ13C, δ15N) during composting of agricultural wastes in relation to compost quality and feedstock

Variations in the relative isotopic abundance of C and N (δ¹³C and δ¹⁵N) were measured during the composting of different agricultural wastes using bench-scale bioreactors. Different mixtures of agricultural wastes (horse bedding manure?+?legume residues; dairy manure?+?jatropha mill cake; dairy manure?+?sugarcane residues; dairy manure alone) were used for aerobic–thermophilic composting. No significant differences were found between the δ¹³C values of the feedstock and the final compost, except for dairy manure?+?sugarcane residues (from initial ratio of ?13.6?±?0.2?‰ to final ratio of ?14.4?±?0.2?‰). δ¹⁵N values increased significantly in composts of horse bedding manure?+?legumes residues (from initial ratio of +5.9?±?0.1?‰ to final ratio of +8.2?±?0.5?‰) and dairy manure?+?jatropha mill cake (from initial ratio of +9.5?±?0.2?‰ to final ratio of +12.8?±?0.7?‰) and was related to the total N loss (mass balance). δ¹³C can be used to differentiate composts from different feedstock (e.g. C₃ or C₄ sources). The quantitative relationship between N loss and δ¹⁵N variation should be determined.     

Effects of the AlN nucleation layer thickness on the crystal structures of an AlN epilayer grown on the 6H-SiC substrate

The influence of the LT-AlN(NL) growth times on the mosaic structure parameters of the AlN layer grown on the LT-AlN(NL)/6H-SiC structures as well as the dislocation densities and the strain behaviours in the AlN epilayers has been investigated using XRD measurements. The growth times of the LT-AlN(NL) were changed to 0, 60, 120, 180, and 240?s. We observed that the mosaic structure parameters of the AlN epilayers were slightly affected by the LT-AlN(NL) growth times. However, the dislocation densities in the AlN layer are affected by the growth times of the LT-AlN(NL) layer. The highest edge dislocation density (5.48?×?10¹⁰?±?2.3?×?10⁹?cm^?2) was measured for the sample in which 120?s grown LT-AlN(NL) was used. On the other hand, highest screw type dislocation density (1.21?×?10¹⁰?±?1.7?×?10⁹?cm^?2) measured in the sample E that contains 240?s growth LT-AlN(NL). The strain calculation results show that the samples without LT-AlN(NL) suffered maximum compressive in-plane strain (?10.9?×?10^?3?±?1.8?×?10^?4), which can be suppressed by increasing the LT-AlN(NL) growth times. The out-of-plane strain also has a compressive character and its values increase with LT-AlN(NL) growth times between 60 and 180?s. Same out-of-plane strain values were measured for the LT-AlN(NL) growth times of 180 and 240?s. Furthermore, the form of the biaxial stress in the AlN epilayer changed from compressive to tensile when the LT-AlN(NL) growth times were greater than 120?s.     

Mechanistic Insights into the Inhibition of Endo-β 1,4 Xyloglucan Hydrolase by a Classical Aspartic Protease Inhibitor

This is the first report of inactivation of xyloglucanase from Thermomonospora sp by pepstatin A, a specific inhibitor towards aspartic proteases. The steady state kinetics revealed a reversible, competitive, two-step inhibition mechanism with IC ₅₀ and K _i values of 3.5?±?0.5 μM and 1.25?±?0.5 μM respectively. The rate constants determined for the isomerization of EI to EI^* and the dissociation of EI* were 14.5?±?1.5?×?10^?5?s^?1 and 2.85?±?1.2?×?10^?8?s^?1 respectively, whereas the overall inhibition constant K _i ^* was 27?±?1 nM. The conformational changes induced upon inhibitor binding to xyloglucanase were monitored by fluorescence analysis and the rate constants derived were in agreement with the kinetic data. The abolished isoindole fluorescence of o-phthalaldehyde (OPTA)-labeled xyloglucanase and far UV analysis suggested that pepstatin binds to the active site of the enzyme. Our results revealed that the inactivation of xyloglucanase is due to the interference in the electronic microenvironment and disruption of the hydrogen-bonding network between the essential histidine and other residues involved in catalysis.     

Interpolated mapping and investigation of environmental radioactivity levels in soils and mushrooms in the Middle Black Sea Region of Turkey

The activity concentration of natural (²³⁸U, ²³²Th, and ⁴⁰K) and artificial (¹³⁷Cs) radionuclides was determined in 50 samples (obtained from the same station) from various species of mushrooms and soil collected from the Middle Black Sea Region (Turkey). The activities of ²³⁸U, ²³²Th, ⁴⁰K, and ¹³⁷Cs were found as 84 ± 16, 45 ± 14, 570 ± 28, and 64 ± 6?Bq?kg^–1 (dry weight), respectively, in the mushroom samples and as 51?±?6, 41?±?6, 201?±?11, and 44?±?4?Bq?kg^–1, respectively, in the soil samples for the entire area of study. The results of all radionuclide activity measurements, except those of ²³⁸U and ²³²Th in the mushroom samples, are consistent with previous studies. In the soil samples, the mean values of ²³⁸U and ²³²Th are above the world mean, and the activity mean of ⁴⁰K is below the world mean. Finally, the activity estimation was made with both the soil and mushroom samples for unmeasured points within the study area by using the ordinary kriging method. Radiological distribution maps were generated.     

Stable carbon and nitrogen isotope discrimination and turnover in a small-bodied insectivorous lizard

Laboratory experiments are useful for estimating the carbon and nitrogen isotope discrimination factors and turnover rates that are critical for drawing field-based inferences on consumer diets using stable isotopes. Although the utility of these discrimination factors is widely recognized, work in terrestrial systems has largely been limited to studies involving mammals and birds. In contrast, scant attention has been paid to the application of isotopic techniques to reptiles, despite their broad diversity in terms of numbers of species as well as their trophic roles. Here we estimate carbon and nitrogen isotope discrimination factors and turnover for the tree lizard (Urosaurus ornatus) using a diet-switch experiment. Lizards were collected from a C₄-dominated grassland and then switched to C₃-based diet (crickets) in the laboratory. We estimated discrimination by lizard claw tissue as Δ¹³C?=?1.2?±?0.1?‰ for carbon and Δ¹⁵N?=?0.7?±?0.1?‰ (mean?±?1 SE) for nitrogen, with 95?% turnover occurring after ～15.5 days. These estimates should be appropriate for use in trophic studies of U. ornatus, and possibly other related small-bodied insectivorous lizards.