Influence of counterions on the structure of bis(oxazoline) copper(II) complexes; an EPR and ENDOR investigation

X- and Q-band EPR and ENDOR spectroscopy was used to study the structure of a series of heteroleptic and homoleptic copper bis(oxazoline) complexes, based on the (−)-2,2′-isopropylidenebis[(4S)-4-phenyl-2-oxazoline] ligand and bearing different counterions (chloride versus triflate); labelled [CuII(1a–c)]. The geometry of the two heteroleptic complexes, [CuII(1a)] and [CuII(1c)], depended on the choice of counterion. Formation of the homoleptic complex was only evident when the CuII(OTf)2 salt was used (CuII(Cl)2 inhibited the transformation from heteroleptic to homoleptic complexes). The hyperfine and quadrupole parameters for the surrounding ligand nuclei were determined by ENDOR. Well resolved 19F and 1H couplings confirmed the presence of both coordinated water and TfO− counterions in [Cu(1a)]

Voice Activated Display of American Sign Language for Airport Security

Conference proceedings from the Technology and Persons with Disabilities Conference-2003. California State University at Northridge, Los Angeles, CA March 17-22, 2003

KELT-10b: The First Transiting Exoplanet from the KELT-South Survey -- A Hot Sub-Jupiter Transiting a V = 10.7 Early G-Star

We report the discovery of KELT-10b, the first transiting exoplanet discovered using the KELT-South telescope. KELT-10b is a highly inflated sub-Jupiter mass planet transiting a relatively bright $V = 10.7$ star (TYC 8378-64-1), with T$_{eff}$ = $5948\pm74$ K, $\log{g}$ = $4.319_{-0.030}^{+0.020}$ and [Fe/H] = $0.09_{-0.10}^{+0.11}$, an inferred mass M$_{*}$ = $1.112_{-0.061}^{+0.055}$ M$_{\odot}$ and radius R$_{*}$ = $1.209_{-0.035}^{+0.047}$ R$_{\odot}$. The planet has a radius R$_{P}$ = $1.399_{-0.049}^{+0.069}$ R$_{J}$ and mass M$_{P}$ = $0.679_{-0.038}^{+0.039}$ M$_{J}$. The planet has an eccentricity consistent with zero and a semi-major axis $a$ = $0.05250_{-0.00097}^{+0.00086}$ AU. The best fitting linear ephemeris is $T_{0}$ = 2457066.72045$\pm$0.00027 BJD$_{TDB}$ and P = 4.1662739$\pm$0.0000063 days. This planet joins a group of highly inflated transiting exoplanets with a radius much larger and a mass much less than those of Jupiter. The planet, which boasts deep transits of 1.4%, has a relatively high equilibrium temperature of T$_{eq}$ = $1377_{-23}^{+28}$ K, assuming zero albedo and perfect heat redistribution. KELT-10b receives an estimated insolation of $0.817_{-0.054}^{+0.068}$ $\times$ 10$^9$ erg s$^{-1}$ cm$^{-2}$, which places it far above the insolation threshold above which hot Jupiters exhibit increasing amounts of radius inflation. Evolutionary analysis of the host star suggests that KELT-10b is unlikely to survive beyond the current subgiant phase, due to a concomitant in-spiral of the planet over the next $\sim$1 Gyr. The planet transits a relatively bright star and exhibits the third largest transit depth of all transiting exoplanets with V $<$ 11 in the southern hemisphere, making it a promising candidate for future atmospheric characterization studies.Comment: 20 pages, 13 figures, 7 tables, accepted for publication in MNRA

Open science in archaeology

No abstract available

Determining the Electronic Confinement of a Subsurface Metallic State

Dopant profiles in semiconductors are important for understanding nanoscale electronics. Highly conductive and extremely confined phosphorus doping profiles in silicon, known as Si:P δ-layers, are of particular interest for quantum computer applications, yet a quantitative measure of their electronic profile has been lacking. Using resonantly enhanced photoemission spectroscopy, we reveal the real-space breadth of the Si:P δ-layer occupied states and gain a rare view into the nature of the confined orbitals. We find that the occupied valley-split states of the δ-layer, the so-called 1Γ and 2Γ, are exceptionally confined with an electronic profile of a mere 0.40 to 0.52 nm at full width at half-maximum, a result that is in excellent agreement with density functional theory calculations. Furthermore, the bulk-like Si 3pz orbital from which the occupied states are derived is sufficiently confined to lose most of its pz-like character, explaining the strikingly large valley splitting observed for the 1Γ and 2Γ states

Oxia Planum: The Landing Site for the ExoMars “Rosalind Franklin” Rover Mission: Geological Context and Prelanding Interpretation

The European Space Agency (ESA) and Roscosmos ExoMars mission will launch the “Rosalind Franklin” rover in 2022 for a landing on Mars in 2023.The goals of the mission are to search for signs of past and present life on Mars, investigate the water/geochemical environment as a function of depth in the shallow subsurface, and characterize the surface environment. To meet these scientific objectives while minimizing the risk for landing, a 5-year-long landing site selection process was conducted by ESA, during which eight candidate sites were down selected to one: Oxia Planum. Oxia Planum is a 200 km-wide low-relief terrain characterized by hydrous clay-bearing bedrock units located at the southwest margin of Arabia Terra. This region exhibits Noachian-aged terrains. We show in this study that the selected landing site has recorded at least two distinct aqueous environments, both of which occurred during the Noachian: (1) a first phase that led to the deposition and alteration of ∼100 m of layered clay-rich deposits and (2) a second phase of a fluviodeltaic system that postdates the widespread clay-rich layered unit. Rounded isolated buttes that overlie the clay-bearing unit may also be related to aqueous processes. Our study also details the formation of an unaltered mafic-rich dark resistant unit likely of Amazonian age that caps the other units and possibly originated from volcanism. Oxia Planum shows evidence for intense erosion from morphology (inverted features) and crater statistics. Due to these erosional processes, two types of Noachian sedimentary rocks are currently exposed. We also expect rocks at the surface to have been exposed to cosmic bombardment only recently, minimizing organic matter damage

Multiple novel prostate cancer susceptibility signals identified by fine-mapping of known risk loci among Europeans

Genome-wide association studies (GWAS) have identified numerous common prostate cancer (PrCa) susceptibility loci. We have fine-mapped 64 GWAS regions known at the conclusion of the iCOGS study using large-scale genotyping and imputation in 25 723 PrCa cases and 26 274 controls of European ancestry. We detected evidence for multiple independent signals at 16 regions, 12 of which contained additional newly identified significant associations. A single signal comprising a spectrum of correlated variation was observed at 39 regions; 35 of which are now described by a novel more significantly associated lead SNP, while the originally reported variant remained as the lead SNP only in 4 regions. We also confirmed two association signals in Europeans that had been previously reported only in East-Asian GWAS. Based on statistical evidence and linkage disequilibrium (LD) structure, we have curated and narrowed down the list of the most likely candidate causal variants for each region. Functional annotation using data from ENCODE filtered for PrCa cell lines and eQTL analysis demonstrated significant enrichment for overlap with bio-features within this set. By incorporating the novel risk variants identified here alongside the refined data for existing association signals, we estimate that these loci now explain ∼38.9% of the familial relative risk of PrCa, an 8.9% improvement over the previously reported GWAS tag SNPs. This suggests that a significant fraction of the heritability of PrCa may have been hidden during the discovery phase of GWAS, in particular due to the presence of multiple independent signals within the same regio

The development and validation of a scoring tool to predict the operative duration of elective laparoscopic cholecystectomy

Background: The ability to accurately predict operative duration has the potential to optimise theatre efficiency and utilisation, thus reducing costs and increasing staff and patient satisfaction. With laparoscopic cholecystectomy being one of the most commonly performed procedures worldwide, a tool to predict operative duration could be extremely beneficial to healthcare organisations. Methods: Data collected from the CholeS study on patients undergoing cholecystectomy in UK and Irish hospitals between 04/2014 and 05/2014 were used to study operative duration. A multivariable binary logistic regression model was produced in order to identify significant independent predictors of long (> 90 min) operations. The resulting model was converted to a risk score, which was subsequently validated on second cohort of patients using ROC curves. Results: After exclusions, data were available for 7227 patients in the derivation (CholeS) cohort. The median operative duration was 60 min (interquartile range 45–85), with 17.7% of operations lasting longer than 90 min. Ten factors were found to be significant independent predictors of operative durations > 90 min, including ASA, age, previous surgical admissions, BMI, gallbladder wall thickness and CBD diameter. A risk score was then produced from these factors, and applied to a cohort of 2405 patients from a tertiary centre for external validation. This returned an area under the ROC curve of 0.708 (SE = 0.013, p  90 min increasing more than eightfold from 5.1 to 41.8% in the extremes of the score. Conclusion: The scoring tool produced in this study was found to be significantly predictive of long operative durations on validation in an external cohort. As such, the tool may have the potential to enable organisations to better organise theatre lists and deliver greater efficiencies in care

Pitfalls in assessing stromal tumor infiltrating lymphocytes (sTILs) in breast cancer

Abstract: Stromal tumor-infiltrating lymphocytes (sTILs) are important prognostic and predictive biomarkers in triple-negative (TNBC) and HER2-positive breast cancer. Incorporating sTILs into clinical practice necessitates reproducible assessment. Previously developed standardized scoring guidelines have been widely embraced by the clinical and research communities. We evaluated sources of variability in sTIL assessment by pathologists in three previous sTIL ring studies. We identify common challenges and evaluate impact of discrepancies on outcome estimates in early TNBC using a newly-developed prognostic tool. Discordant sTIL assessment is driven by heterogeneity in lymphocyte distribution. Additional factors include: technical slide-related issues; scoring outside the tumor boundary; tumors with minimal assessable stroma; including lymphocytes associated with other structures; and including other inflammatory cells. Small variations in sTIL assessment modestly alter risk estimation in early TNBC but have the potential to affect treatment selection if cutpoints are employed. Scoring and averaging multiple areas, as well as use of reference images, improve consistency of sTIL evaluation. Moreover, to assist in avoiding the pitfalls identified in this analysis, we developed an educational resource available at www.tilsinbreastcancer.org/pitfalls