Determination of Uranium and Thorium in Zircon,Apatite, and Fluorite: Application to Laser (U-Th)/He Thermochronology

We have developed a methodology for (U-Th)/He thermochronology on a variety of mineral species. With many laboratories initiating research in the area of (U-Th)/He thermochronology, we recognize that there may be interest in a review of analytical procedures for uranium and thorium determination in single crystals of apatite, zircon, rutile, and fluorite. Uranium and thorium are both determined by inductively coupled plasma mass-spectrometry using an isotope dilution method. While standard and spike solutions can be purchased, their isotopic composition and the concentration of the standard solution need to be verified. Digestion procedures for apatite and fluorite are relatively straightforward, but zircon decomposition requires the use of pressure vessels or fusion. Matrix effects are shown to have an insignificant effect on isotope ratios, although isobaric interferences, particularly of PtAr⁺ on U isotopes, can be a problem. We include complete thermochronology datasets for replicate analysis of Durango apatite, Yucca Mountain fluorite, and an Australian megacryst zircon.     

Combined Photoredox and Carbene Catalysis for the Synthesis of Ketones from Carboxylic Acids

As a key element in the construction of complex organic scaffolds, the formation of C?C bonds remains a challenge in the field of synthetic organic chemistry. Recent advancements in single‐electron chemistry have enabled new methods for the formation of various C?C bonds. Disclosed herein is the development of a novel single‐electron reduction of acyl azoliums for the formation of ketones from carboxylic acids. Facile construction of the acyl azolium in situ followed by a radical–radical coupling was made possible merging N‐heterocyclic carbene (NHC) and photoredox catalysis. The utility of this protocol in synthesis was showcased in the late‐stage functionalization of a variety of pharmaceutical compounds. Preliminary investigations using chiral NHCs demonstrate that enantioselectivity can be achieved, showcasing the advantages of this protocol over alternative methodologies.     

Beat-to-beat respiratory motion correction with near 100% efficiency: a quantitative assessment using high-resolution coronary artery imaging

This study quantitatively assesses the effectiveness of retrospective beat-to-beat respiratory motion correction (B2B-RMC) at near 100% efficiency using high-resolution coronary artery imaging. Three-dimensional (3D) spiral images were obtained in a coronary respiratory motion phantom with B2B-RMC and navigator gating. In vivo, targeted 3D coronary imaging was performed in 10 healthy subjects using B2B-RMC spiral and navigator gated balanced steady-state free-precession (nav-bSSFP) techniques. Vessel diameter and sharpness in proximal and mid arteries were used as a measure of respiratory motion compensation effectiveness and compared between techniques. Phantom acquisitions with B2B-RMC were sharper than those acquired with navigator gating (B2B-RMC vs. navigator gating: 1.01±0.02 mm⁻¹ vs. 0.86±0.08 mm⁻¹, P<.05). In vivo B2B-RMC respiratory efficiency was significantly and substantially higher (99.7%±0.5%) than nav-bSSFP (44.0%±8.9%, P<.0001). Proximal and mid vessel sharpnesses were similar (B2B-RMC vs. nav-bSSFP, proximal: 1.00±0.14 mm⁻¹ vs. 1.08±0.11 mm⁻¹, mid: 1.01±0.11 mm⁻¹ vs. 1.05±0.12 mm⁻¹; both P=not significant [ns]). Mid vessel diameters were not significantly different (2.85±0.39 mm vs. 2.80±0.35 mm, P=ns), but proximal B2B-RMC diameters were slightly higher (2.85±0.38 mm vs. 2.70±0.34 mm, P<.05), possibly due to contrast differences. The respiratory efficiency of B2B-RMC is less variable and significantly higher than navigator gating. Phantom and in vivo vessel sharpness and diameter values suggest that respiratory motion compensation is equally effective.     

Is There an Effect of Dysphonic Teachers' Voices on Children's Processing of Spoken Language?

There is a vast body of literature on the causes, prevalence, implications, and issues of vocal dysfunction in teachers. However, the educational effect of teacher vocal impairment is largely unknown. The purpose of this study was to investigate the effect of impaired voice quality on children's processing of spoken language. One hundred and seven children (age range, 9.2 to 10.6, mean 9.8, SD 3.76 months) listened to three video passages, one read in a control voice, one in a mild dysphonic voice, and one in a severe dysphonic voice. After each video passage, children were asked to answer six questions, with multiple-choice answers. The results indicated that children's perceptions of speech across the three voice qualities differed, regardless of gender, IQ, and school attended. Performance in the control voice passages was better than performance in the mild and severe dysphonic voice passages. No difference was found between performance in the mild and severe dysphonic voice passages, highlighting that any form of vocal impairment is detrimental to children's speech processing and is therefore likely to have a negative educational effect. These findings, in light of the high rate of vocal dysfunction in teachers, further support the implementation of specific voice care education for those in the teaching profession.     

Physical characterization of uranium oxide pellets and powder applied in the Nuclear Forensics International Technical Working Group Collaborative Materials Exercise 4

Journal of Radioanalytical and Nuclear Chemistry - Physical characterization is one of the most broad and important categories of techniques to apply in a nuclear forensic examination. Physical...     

Decomposition of in vivo spatially offset Raman spectroscopy data using multivariate analysis techniques

The decomposition of spatially offset Raman spectra for complex multilayer systems, such as biological tissues, requires advanced techniques such as multivariate analyses. Often, in such situations, the decomposition methods can reach their limits of accuracy well before the limits imposed by signal‐to‐noise ratios. Consequently, more effective reconstruction methods could yield more accurate results with the same data set. In this study we process spatially offset Raman spectroscopy (SORS) data with three different multivariate techniques (band‐target entropy minimization (BTEM), multivariate curve resolution and parallel factor analysis (PARAFAC)) and compare their performance when analysing a spectrally challenging plastic model system and an even more challenging problem, the analysis of human bone transcutaneously in vivo. For the in vivo measurements, PARAFAC's requirement of multidimensional orthogonal data is addressed by recording SORS spectra both at different spatial offsets and at different anatomical points, the latter providing added dimensionality through the variation of skin/soft tissue thickness. The BTEM and PARAFAC methods performed the best on the plastic system with the BTEM more faithfully reconstructing the major Raman bands and PARAFAC the smaller more heavily overlapped features. All three methods succeeded in reconstructing the bone spectrum from the transcutaneous data and gave good figures for the phosphate‐to‐carbonate ratio (within 2% of excised human tibia bone); the PARAFAC gave the most accurate figure for the mineral‐to‐collagen ratio (20% less than excised human tibia bone). Previous studies of excised bones have shown that certain bone diseases (such as osteoarthritis, osteoporosis and osteogenesis imperfecta) are accompanied by compositional abnormalities that can be detected with Raman spectroscopy, the utility of a technique which could reconstruct bone spectra accurately is manifest. The results have relevance on the use of SORS in general. © 2014 Crown copyright. Journal of Raman Spectroscopy published by John Wiley & Sons, Ltd.     

Combined Photoredox and Carbene Catalysis for the Synthesis of Ketones from Carboxylic Acids**

As a key element in the construction of complex organic scaffolds, the formation of C−C bonds remains a challenge in the field of synthetic organic chemistry. Recent advancements in single-electron chemistry have enabled new methods for the formation of various C−C bonds. Disclosed herein is the development of a novel single-electron reduction of acyl azoliums for the formation of ketones from carboxylic acids. Facile construction of the acyl azolium in situ followed by a radical–radical coupling was made possible merging N-heterocyclic carbene (NHC) and photoredox catalysis. The utility of this protocol in synthesis was showcased in the late-stage functionalization of a variety of pharmaceutical compounds. Preliminary investigations using chiral NHCs demonstrate that enantioselectivity can be achieved, showcasing the advantages of this protocol over alternative methodologies.     

The application of radiochronometry during the 4th collaborative materials exercise of the nuclear forensics international technical working group (ITWG)

Journal of Radioanalytical and Nuclear Chemistry - In a recent international exercise, 10 international nuclear forensics laboratories successfully performed radiochronometry on three low enriched...