Ab initio pseudopotential study of vacancies and self-interstitials in hcp titanium

By means of an ab initio plane-wave pseudopotential method, monovacancy, divacancy and self-interstitials in hcp titanium are investigated. The calculated monovacancy formation energy is 1.97 eV, which is in excellent agreement with other theoretical calculations, and agrees qualitatively with published experimental results. The relaxation of the atoms around a single vacancy is observed to be small. Two divacancy configurations, the in-plane and the off-plane, have also been shown to be equally stable. With regards to the interstitials, of the eight configurations studied, two (octahedral and basal octahedral) have relatively lower formation energies and are, thus, the most likely stable configurations. We find small energy differences between them, suggesting their possible co-existence. It is also observed that the tetrahedral configuration decays to a split dumbbell configuration, whereas both the basal tetrahedral and the basal pseudocrowdion interstitials decay to the basal octahedral configuration. Using the nudged elastic band method (NEB), we determine a possible minimum energy path (MEP) for the diffusion of self-interstitial titanium atoms from an octahedral site to the nearest octahedral site. The energy barrier for this migration mechanism is shown to be about 0.20 eV.     

Catalytic Desymmetric Cycloaddition of Diaziridines with Metalloenolcarbenes: The Role of Donor–Acceptor Cyclopropenes

A chiral copper(I) complex catalyzes reactions of symmetric diaziridines with enol diazo compounds, which react through N?N bond ring opening in a formal [3+3] cycloaddition to form four chiral centers with high stereocontrol. A broad spectrum of bridged dinitrogen heterocycles were obtained in high yields and excellent diastereo‐ and enantioselectivities from γ‐substituted enol diazoacetates, while their geometrical isomers gave different enantioselectivities. Donor–acceptor cyclopropenes formed from the geometrical isomers of the γ‐substituted enol diazoacetates underwent catalytic ring opening to give only the Z isomer of the metalloenolcarbene intermediate, provided excellent yields and selectivities for the 1,5‐diazabicyclo[n.3.1]non‐2‐ene derivatives.     

Highly Selective Optical Detection of Fe3+ Ions in Aqueous Solution Using Label‐Free Silicon Nanocrystals

High brightness amine‐terminated silicon nanocrystals (Si NCs) have been utilized in a simple and rapid assay for the highly selective and sensitive detection of Fe³⁺ via quenching of their strong blue luminescence, without the need for analyte‐specific labeling groups. Sensitive detection of Fe³⁺ is successfully demonstrated, with a linear relationship observed between luminescence quenching and Fe³⁺ concentration from 5 × 10^?6 to 900 × 10^?6m and a limit of detection of 1.3 × 10^?6m . The Si NCs show excellent selectivity toward Fe³⁺ ions, with no quenching of the luminescence signal induced by the presence of Fe²⁺ ions, allowing for solution phase discrimination between the ionic species in different charge states.     

A rapid dissolution procedure to aid initial nuclear forensics investigations of chemically refractory compounds and particles prior to gamma spectrometry

A rapid and effective preparative procedure has been evaluated for the accurate determination of low-energy (40–200 keV) gamma-emitting radionuclides (²¹⁰Pb, ²³⁴Th, ²²⁶Ra, ²³⁵U) in uranium ores and uranium ore concentrates (UOCs) using high-resolution gamma ray spectrometry. The measurement of low-energy gamma photons is complicated in heterogeneous samples containing high-density mineral phases and in such situations activity concentrations will be underestimated. This is because attenuation corrections, calculated based on sample mean density, do not properly correct where dense grains are dispersed within a less dense matrix (analogous to a nugget effect). The current method overcomes these problems using a lithium tetraborate fusion that readily dissolves all components including high-density, self-attenuating minerals/compounds. This is the ideal method for dissolving complex, non-volatile components in soils, rocks, mineral concentrates, and other materials where density reduction is required. Lithium borate fusion avoids the need for theoretical efficiency corrections or measurement of matrix matched calibration standards. The resulting homogeneous quenched glass produced can be quickly dissolved in nitric acid producing low-density solutions that can be counted by gamma spectrometry. The effectiveness of the technique is demonstrated using uranium-bearing Certified Reference Materials and provides accurate activity concentration determinations compared to the underestimated activity concentrations derived from direct measurements of a bulk sample. The procedure offers an effective solution for initial nuclear forensic studies where complex refractory minerals or matrices exist. It is also significantly faster, safer and simpler than alternative approaches.     

Total Synthesis,Stereochemical Assignment,and Field‐Testing of the Sex Pheromone of the Strepsipteran Xenos peckii

The sex pheromone of the endoparasitoid insect Xenos peckii (Strepsiptera: Xenidae) was recently identified as (7E,11E)‐3,5,9,11‐tetramethyl‐7,11‐tridecadienal. Herein we report the asymmetric synthesis of three candidate stereostructures for this pheromone using a synthetic strategy that relies on an sp³–sp² Suzuki–Miyaura coupling to construct the correctly configured C7‐alkene function. Comparison of ¹H NMR spectra derived from the candidate stereostructures to that of the natural sex pheromone indicated a relative configuration of (3R*,5S*,9R*). Chiral gas chromatographic (GC) analyses of these compounds supported an assignment of (3R,5S,9R) for the natural product. Furthermore, in a 16‐replicate field experiment, traps baited with the synthetic (3R,5S,9R)‐enantiomer alone or in combination with the (3S,5R,9S)‐enantiomer captured 23 and 18 X. peckii males, respectively (mean±SE: 1.4±0.33 and 1.1±0.39), whereas traps baited with the synthetic (3S,5R,9S)‐enantiomer or a solvent control yielded no captures of males. These strong field trapping data, in combination with spectroscopic and chiral GC data, unambiguously demonstrate that (3R,5S,9R,7E,11E)‐3,5,9,11‐tetramethyl‐7,11‐tridecadienal is the X. peckii sex pheromone.     

International inter-comparison exercise on $${}^{153}\hbox {Sm}$$

Samarium-153 (\({}^{153}\hbox {Sm}\)) is a short-lived radionuclide that decays to stable europium-153 via beta emission, with subsequent de-excitation via gamma emission and internal conversion. Historical measurements of \({}^{153}\hbox {Sm}\) by gamma spectrometry and beta liquid scintillation counting have shown a low bias compared to beta proportional counting. In order to investigate this, four national laboratories jointly conducted an experimental inter-comparison exercise on a certified \({}^{153}\hbox {Sm}\) sample, created from neutron activation of samarium-152. Radiometric measurements were conducted using gamma spectrometry, liquid scintillation counting, gas proportional counting, and passivated implanted planar silicon detectors and compared across the four institutions against the certified value. The results from this experiment are presented together with a number of conclusions which suggest that the current published cumulative fission yield for \({}^{153}\hbox {Sm}\), as used by many laboratories, is approximately 15% high and is the likely cause of the previously observed bias.     

Optical parametric oscillation in periodically poled lithium niobate driven by a diode-pumped Q-switched erbium fiber laser

We describe what is to our knowledge the first nanosecond periodically poled lithium niobate (PPLN) optical parametric oscillator (OPO) driven by a fiber laser. The source was frequency doubled by a PPLN sample before pumping a second, 20-mm-long, PPLN crystal. The OPO threshold was <10muJ, with pump depletions of as much as 45% and a tunable signal range of 945-1450 nm (1690-4450-nm idler range). We demonstrated 130-nm signal tuning by varying the pump wavelength and doubling crystal's temperature. Also, we achieved 15-nm tuning with all crystals at a constant temperature. The results demonstrate the potential of the fiber laser:PPLN combination for practical, versatile, and tunable sources.