Silver(i) Perfluoroalcoholates: Synthesis, Structure, and their Use as Transfer Reagents

Herein we report a general access to silver(i) perfluoroalcoholates, their structure in the solid state and in solution, and their use as transfer reagents. The silver(i) perfluoroalcoholates are prepared by the reaction of AgF with the corresponding perfluorinated carbonyl compounds in acetonitrile and are stable for a prolonged time at –18 °C. X-Ray analysis of single crystals of perfluoroalcoholate species showed that two Ag(i) centers are bridged by the alcoholate ligands. In acetonitrile solution, Ag[OCF3] forms different structures as indicated by IR spectroscopy. Furthermore, the silver(i) perfluoroalcoholates can be used as easy-to-handle transfer reagents for the synthesis of Cu[OCF3], Cu[OC2F5], [PPh4][Au(CF3)3(OCF3)], and fluorinated alkyl ethers

Physiologic artifacts in resting state oscillations in young children: methodological considerations for noisy data

We quantified the potential effects of physiologic artifact on the estimation of EEG band power in a cohort of typically developing children in order to guide artifact rejection methods in quantitative EEG data analysis in developmental populations. High density EEG was recorded for 2 min while children, ages 2–6, watched a video of bubbles. Segments of data were categorized as blinks, saccades, EMG or artifact-free, and both absolute and relative power in the theta (4–7 Hz), alpha (8–12 Hz), beta (13–30 Hz) and gamma (35–45 Hz) bands were calculated in 9 regions for each category. Using a linear mixed model approach with artifact type, region and their interaction as predictors, we compared mean band power between clean data and each type of artifact. We found significant differences in mean relative and absolute power between artifacts and artifact-free segments in all frequency bands. The magnitude and direction of the differences varied based on power type, region, and frequency band. The most significant differences in mean band power were found in the gamma band for EMG artifact and the theta band for ocular artifacts. Artifact detection strategies need to be sensitive to the oscillations of interest for a given analysis, with the most conservative approach being the removal of all EMG and ocular artifact from EEG data. Quantitative EEG holds considerable promise as a clinical biomarker of both typical and atypical development. However, there needs to be transparency in the choice of power type, regions of interest, and frequency band, as each of these variables are differentially vulnerable to noise, and therefore, their interpretation depends on the methods used to identify and remove artifacts

Life cycle impacts assessment of two gold extraction systems in Colombia : open-pit and alluvial mining

Purpose: Gold mining has historically and significantly contributed to the Colombian economy. Gold extraction in Colombia is mainly done through two techniques: open-pit and alluvial mining. In this study, the environmental impacts of both these mining systems were analyzed using the life cycle assessment (LCA) framework, including identification of the system components that contribute most to impacts. Methods: Inventory data were obtained for two medium-scale mines in Colombia, one representing the open-pit method and the other the alluvial method. Environmental impacts were classified and characterized by mid-point impact categories and further aggregated into end-point indicators through the ReCiPe (v. 1.11) methodology, which uses a hierarchist perspective. Results: Results for end-point indicators show that the open-pit mining presents higher values in the human health damage category, influenced primarily by tailings and by the excavation process. For the alluvial mining, the overall impacts were an order of magnitude lower, with ecosystem quality as the most significant contributor due to the stripping of soil and vegetation. In the case of mid-point indicators, freshwater and marine ecotoxicity contribute the most to open-pit mining, while for alluvial mining, metal depletion and natural land transformation contribute the most. Climate change is also a significant impact category for alluvial and open-pit mining. Conclusions: The is a substantial difference in environmental impacts between the two mining systems: the quantified total environmental impact was 1.0 × 1004 points for the open-pit mine and 2.4 × 1003 points for the alluvial mine. Since these mines represent specific Colombian operational conditions, this conclusion cannot be confidently extended to other operational contexts. For example, results in other cases may depend on the local geological features and natural environment conditions. Knowing the critical mining supply chain stages for environmental performance will allow the decision-makers to provide the tools for more sustainable extraction and production

Evolution of the early to late Archean mantle from Hf-Nd-Ce isotope systematics in basalts and komatiites from the Pilbara Craton

Inferences on the early evolution of the Earth's mantle can be deduced from long-lived radiogenic isotope Lu-176-Hf-176 and systems such as Sm-147-Nd-143, for which both parent and daughter elements largely remain immobile at low metamorphic grades. However, it remains ambiguous when and to what extent mantle-crust differentiation processes had started in the Archean. For a better understanding of Archean mantle-crust evolution, we determined the initial Lu-176-Hf-176, Sm-147-Nd-143, and, in a new approach, the La-138-Ce-138 isotope compositions of a suite of Archean mafic-ultramafic rock samples from the 3.53-2.83 Ga old Pilbara Craton and 2.78-2.63 Ga old Fortescue Group in NW Australia. These rocks represent one of the best-preserved Archean successions worldwide and contain mafic-ultramafic rocks that were erupted during repeated and long-lived pulses of volcanism throughout much of the Archean. Mantlederived mafic-ultramafic rock samples were collected from six major stratigraphic groups of the Pilbara Craton and the overlying Fortescue Group in order to characterize the parental mantle source regions of the lavas and to reconstruct the temporal evolution of the ambient mantle beneath this piece of cratonic lithosphere. In addition, we analyzed contemporaneous TTG-like igneous suites and interbedded sediments in order to reconstruct the lithospheric evolution of the Pilbara Craton. The Hf-Nd-Ce isotope data imply the onset of mantle-crust differentiation in the Pilbara Craton as early as similar to 4.2 Ga, well prior to any of the preserved stratigraphy. Within error, coupled Ce-Nd-Hf isotope arrays all intersect chondritic values, implying that the Earth is of broadly chondritic composition, also for the La-138-Ce-138 isotope system. Mafic rocks usually yield strongly coupled epsilon Hf-(i), epsilon Nd-(i) and epsilon Ce-(i) values that form a mixing line between an evolving depleted upper mantle composition and the primitive mantle value (epsilon Hf-(i) ca. 0.0 to + 3.2, epsilon Nd-(i) ca. +0.2 to +1.7 and epsilon Ce-(i) ca. +0.3 to -0.1). As all Paleoarchean samples lack co-variations between Nb/Th with epsilon Hf-(i) or epsilon Nd-(i), contamination with an enriched crust is unlikely to explain this mixing trend. The most primitive mantle-like mafic samples show elevated Gd-N/Yb-N ratios (2.2-1.4), implying the involvement of a deep-rooted, near-primitive, upwelling mantle that was progressively mixed into the depleted upper mantle. In contrast to the mafic rocks, most, but not all komatiites are decoupled in their initial Hf-Nd-Ce isotope compositions, by having extremely radiogenic epsilon Hf-(i) values at only moderately high epsilon Nd-(i) and low epsilon Ce-(i) values. This decoupling is best explained by the assimilation of mantle domains that underwent early melt depletion in the garnet stability field and evolved at high Lu-176/Hf-176 ratios but at moderate Sm-147/Nd-143 and La-138/Ce-138 ratios over time. The disappearance of rocks with decoupled Hf-Nd isotope compositions after similar to 3.2 Ga is likely linked to decreasing mantle temperatures that were no longer able to melt such refractory mantle domains. Collectively, our new data for mafic rocks from the Pilbara Craton confirm the presence of long-term depleted mantle domains in the early Archean that are not sampled by the zircon Hf isotope record in the Pilbara Craton. (C) 2020 The Authors. Published by Elsevier B.V

Reader Perceptions and Impact of AI on CT Assessment of Air Trapping

Quantitative imaging measurements can be facilitated by artificial intelligence (AI) algorithms, but how they might impact decision-making and be perceived by radiologists remains uncertain. After creation of a dedicated inspiratory-expiratory CT examination and concurrent deployment of a quantitative AI algorithm for assessing air trapping, five cardiothoracic radiologists retrospectively evaluated severity of air trapping on 17 examination studies. Air trapping severity of each lobe was evaluated in three stages: qualitatively (visually); semiquantitatively, allowing manual region-of-interest measurements; and quantitatively, using results from an AI algorithm. Readers were surveyed on each case for their perceptions of the AI algorithm. The algorithm improved interreader agreement (intraclass correlation coefficients: visual, 0.28; semiquantitative, 0.40; quantitative, 0.84; P < .001) and improved correlation with pulmonary function testing (forced expiratory volume in 1 second-to-forced vital capacity ratio) (visual r = -0.26, semiquantitative r = -0.32, quantitative r = -0.44). Readers perceived moderate agreement with the AI algorithm (Likert scale average, 3.7 of 5), a mild impact on their final assessment (average, 2.6), and a neutral perception of overall utility (average, 3.5). Though the AI algorithm objectively improved interreader consistency and correlation with pulmonary function testing, individual readers did not immediately perceive this benefit, revealing a potential barrier to clinical adoption. Keywords: Technology Assessment, Quantification © RSNA, 2021