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We assess the binding of C2H4 to the coordinately unsaturated copper(I) sites of the metal-organic frameworks Cu(I)-ZrTpmC* and Cu(I)-MFU-4l via 13C solid-state nuclear magnetic resonance spectroscopy, density functional theory (DFT), and natural localized molecular orbital (NLMO) analysis. Using these methods, forward-donation and back-donation contributions between C2H4 and the exposed Cu(I) are delineated and high-binding enthalpies are contextualized as a function of electronic changes upon site modification and adsorption. With the infrastructure for DFT and solid-state 13C NMR becoming more routine for scientists, we envision these results will support the study of exposed electron-rich metal sites in a variety of chemical applications.

Coordinatively unsaturated metal sites within certain zeolites and metal-organic frameworks can strongly adsorb a wide array of substrates. While many classical examples involve electron-poor metal cations that interact with adsorbates largely through physical interactions, unsaturated electron-rich metal centers housed within porous frameworks can often chemisorb guests amenable to redox activity or covalent bond formation. Despite the promise that materials bearing such sites hold in addressing myriad challenges in gas separations and storage, very few studies have directly interrogated mechanisms of chemisorption at open metal sites within porous frameworks. Here, we show that nondissociative chemisorption of H2 at the trigonal pyramidal Cu+ sites in the metal-organic framework CuI-MFU-4l occurs via the intermediacy of a metastable physisorbed precursor species. In situ powder neutron diffraction experiments enable crystallographic characterization of this intermediate, the first time that this has been accomplished for any material. Evidence for a precursor intermediate is also afforded from temperature-programmed desorption and density functional theory calculations. The activation barrier separating the precursor species from the chemisorbed state is shown to correlate with a change in the Cu+ coordination environment that enhances π-backbonding with H2. Ultimately, these findings demonstrate that adsorption at framework metal sites does not always follow a concerted pathway and underscore the importance of probing kinetics in the design of next-generation adsorbents.

We provide an overview of the design and capabilities of the near-infrared spectrograph (NIRSpec) onboard the James Webb Space Telescope. NIRSpec is designed to be capable of carrying out low-resolution ($R\!=30\!-330$) prism spectroscopy over the wavelength range $0.6-5.3\!~\mu$m and higher resolution ($R\!=500\!-1340$ or $R\!=1320\!-3600$) grating spectroscopy over $0.7-5.2\!~\mu$m, both in single-object mode employing any one of five fixed slits, or a 3.1$\times$3.2 arcsec$^2$ integral field unit, or in multiobject mode employing a novel programmable micro-shutter device covering a 3.6$\times$3.4~arcmin$^2$ field of view. The all-reflective optical chain of NIRSpec and the performance of its different components are described, and some of the trade-offs made in designing the instrument are touched upon. The faint-end spectrophotometric sensitivity expected of NIRSpec, as well as its dependency on the energetic particle environment that its two detector arrays are likely to be subjected to in orbit are also discussed., Comment: Accepted for publication in A&A. 22 pages, 19 figures

In this 2022 Update of Version 2020 of the VI Consensus of the Brazilian Society of Bone Marrow Transplantation (SBTMO) for Graft-versus-Host-Disease (GVHD), we seek to provide evidence-based guidance on all the novel and clinically relevant advancements in both prophylaxis and therapy of Graft-versus-Host Disease for all of those who delve into the field of Hematopoietic Stem Cell Transplantation.

The quest to develop materials that enable the manufacture of dimensionally ultra-stable structures for critical-dimension components in spacecraft has led to much research over many decades and the evolution of carbon fibre reinforced polymer materials. This has resulted in structural designs that feature a near-zero coefficient of thermal expansion. However, the dimensional instabilities that result from moisture ingression and release remain the fundamental vulnerability of the matrix, which restricts many applications. Here, we address this challenge by developing a space-qualifiable physical surface barrier that blends within the mechanical properties of the composite, thus becoming part of the composite itself. The resulting enhanced composite features mechanical integrity and a strength that is superior to the underlying composite, while remaining impervious to moisture and outgassing. We demonstrate production capability for a model-sized component for the Sentinel-5 mission and demonstrate such capability for future European Space Agency (ESA) and National Aeronautics and Space Administration (NASA) programmes such as Copernicus Extension, Earth Explorer and Science Cosmic Visions. Multiple layers of diamond-like carbon films are shown to act as moisture barriers when conformally deposited on carbon fibre reinforced polymers used in space applications.

Coordinatively unsaturated metal sites within certain zeolites and metal-organic frameworks can strongly adsorb a wide array of substrates. While many classical examples involve electron-poor metal cations that interact with adsorbates largely through physical interactions, unsaturated electron-rich metal centers housed within porous frameworks can often chemisorb guests amenable to redox activity or covalent bond formation. Despite the promise that materials bearing such sites hold in addressing myriad challenges in gas separations and storage, very few studies have directly interrogated mechanisms of chemisorption at open metal sites within porous frameworks. Here, we show that nondissociative chemisorption of H

Coordinatively-unsaturated metal sites within certain zeolites and metal–organic frameworks can strongly adsorb various molecules. While many classical examples involve electron-poor metal cations that interact with adsorbates largely through electrostatic interactions, unsaturated electron-rich metal centers housed within porous frameworks can often chemisorb guests amenable to redox activity or covalent bond formation. Despite the promise that materials bearing such sites hold in addressing myriad challenges in gas separations and storage, very few studies have directly interrogated mechanisms of chemisorption at open metal sites within porous frameworks. Here, we show that H2chemisorption at the trigonal pyramidal Cu+sites in the metal–organic framework CuI‑MFU-4l occurs via the intermediacy of a metastable physisorbed precursor species. In situpowder neutron diffraction experiments enable crystallographic characterization of this intermediate, the first time that this has been accomplished for any material. Support for a precursor intermediate is also afforded from temperature-programmed desorption and density functional theory calculations. The activation barrier separating the precursor species from the chemisorbed state is shown to correlate with a change in the Cu+coordination environment that enhances π-backbonding with H2. Ultimately, these findings demonstrate that adsorption at framework metal sites does not always follow a concerted pathway and underscore the importance of probing kinetics in the design of next-generation adsorbents.

Where they are present in catchments, peatlands are a dominant source of dissolved organic matter (DOM) to surrounding waterways due, in part, to high production rates. Despite the preponderance of peatlands in northern latitudes and expected peatland vulnerability to climate change, little is known about peatland DOM degradation relative to a more comprehensive understanding of degradation when DOM is sourced from upland-dominated catchments. We compared DOM biodegradability of various sources of stream water in two catchments having peatlands (22%–33% of the area) surrounded by upland forests (70%–90% of the area, either deciduous or coniferous). We measured total organic carbon (TOC), and biodegradable dissolved organic carbon concentrations; bacterial respiration rates; streamflow; and upland runoff during and after snowmelt (March to June, 2009–2011). We also explored if DOM in upland runoff stimulated biodegradation of peatland-derived DOM (i.e., a priming effect), and if forest cover type affected DOM biodegradability. As expected, the peatlands were the largest sources of both water (72%–80%) and TOC (92%– 96%) to the streams although more area in each catchment was in uplands (70%– 90%). Several results were unexpected, yet revealing: (1) DOM from peatlands sometimes had the same biodegradability as DOM from uplands, (2) upland sources of DOM had negligible effects on biodegradability in the peatland and downstream, and (3) upland deciduous cover did not yield more degradable DOM than conifer cover. The most pronounced effect of upland runoff was dilution of downstream TOC concentrations when there was upland runoff. Overall, the effects of upland DOM may have been negligible due to the overriding effect of the large amount of biodegradable DOM that originated in bogs. This research highlights that peatland-sourced DOM has important effects on downstream DOM biodegradability even in catchments where upland area is substantially larger than peatland area.

VEGF blockade does not uniformly result in clinical benefit. We evaluated safety, dose-limiting toxicities (DLT), recommended phase II dose (RP2D), antitumor efficacy, and exploratory biomarkers including pharmacogenomics and pharmacokinetics with sorafenib, bevacizumab, and paclitaxel in patients with refractory cancers. The study had a “3 + 3” design, using paclitaxel 80 mg/m2 every week for 3 weeks, in every 4 week cycles, bevacizumab 5 mg/kg every 2 weeks, and sorafenib 200 or 400 mg twice a day, 5 or 7 days/week (5/7, 7/7). The MTD cohort was expanded. Twenty-seven patients enrolled in 3 cohorts: sorafenib 200 mg twice a day 5/7, 200 mg twice a day 7/7, and 400 mg twice a day 5/7. DLTs were grade 3 neutropenia >7 days (cohort 1, 1), grade 3 hypertension (cohort 2, 1), grade 3 hand–foot skin reaction (HFSR; cohort 3, 2). MTD was sorafenib 200 mg twice a day 7/7. Six DLTs occurred in cohort 2 expansion: grade 3 HFSR (2), grade 2 HFSR with sorafenib delay >7 days (2), grade 4 cerebrovascular accident (1), grade 3 neutropenia >7 days (1). RP2D was sorafenib 200 mg twice a day 5/7. Most patients (62%) dose reduced sorafenib to 200 mg daily 5/7 after a median 3 (range, 2–17) cycles. Response rates were 48% overall (27) and 64% for ovarian cancers (14). VEGF-A-1154AA and -7TT recessive homozygous genotypes conferred worse overall survival versus alternative genotypes (7 vs. 22 months). Intermittent, low-dose sorafenib (200 mg twice a day 5/7) combined with bevacizumab and paclitaxel was tolerable and had high antitumor efficacy in patients with refractory cancer (NCT00572078).

The quest to develop materials that enable the manufacture of dimensionally ultra-stable structures for critical-dimension components in spacecraft has led to much research over many decades and the evolution of carbon fibre reinforced polymer materials. This has resulted in structural designs that feature a near-zero coefficient of thermal expansion. However, the dimensional instabilities that result from moisture ingression and release remain the fundamental vulnerability of the matrix, which restricts many applications. Here, we address this challenge by developing a space-qualifiable physical surface barrier that blends within the mechanical properties of the composite, thus becoming part of the composite itself. The resulting enhanced composite features mechanical integrity and a strength that is superior to the underlying composite, while remaining impervious to moisture and outgassing. We demonstrate production capability for a model-sized component for the Sentinel-5 mission and demonstrate such capability for future European Space Agency (ESA) and National Aeronautics and Space Administration (NASA) programmes such as Copernicus Extension, Earth Explorer and Science Cosmic Visions.

Background It is challenging to find an iron compound that combines good bioavailability with minimal sensory changes when added to seasonings or condiments. Ferric pyrophosphate (FePP) is currently used to fortify bouillon cubes, but its bioavailability is generally low. Previously, the addition of a stabilizer, sodium pyrophosphate (NaPP), improved iron bioavailability from a bouillon drink. Objective We assessed whether there is a dose-response effect of added NaPP on iron bioavailability from local meals prepared with intrinsically labeled FePP-fortified bouillon cubes in young Nigerian women using iron stable isotope techniques. Methods In a double-blind, randomized, cross-over trial, women (n = 24; aged 18–40 y; mean BMI 20.5 kg/m2) consumed a Nigerian breakfast and lunch for 5 d prepared with bouillon cubes containing 2.5 mg 57Fe (as FePP) and 3 different molar ratios of NaPP: 57Fe (0:1, 3:1, and 6:1). Iron bioavailability was assessed by measuring 57Fe incorporation into erythrocytes 16 d after each 5 d NaPP: 57Fe feeding period. Data were analyzed using a linear regression model of log iron absorption on NaPP ratio, with body weight and baseline body iron stores as covariates and subject as a random intercept. Results Of the women included, 46% were anemic and 26% were iron deficient. Iron bioavailability was 10.8, 9.8, and 11.0% for the 0:1, 3:1, and 6:1 NaPP:57Fe treatments, respectively. There was no dose-response effect of an increasing NaPP:57Fe ratio (β ± SE: 0.003 ± 0.028, P = 0.45). Conclusions In this study, the addition of NaPP did not increase iron bioavailability from FePP-fortified bouillon cubes. However, iron bioavailability from the Nigerian meals prepared with FePP-fortified bouillon cubes was higher than expected. These results are encouraging for the potential of bouillon cubes as a fortification vehicle. Further studies are needed to assess the effect of FePP-fortified bouillon cubes on improving iron status in low-income populations. This trial was registered at clinicaltrials.gov as NCT02815449., The Journal of Nutrition, 149 (5), ISSN:0022-3166, ISSN:1541-6100

We subjectively perceive our visual field with high fidelity, yet peripheral distortions can go unnoticed and peripheral objects can be difficult to identify (crowding). Prior work showed that humans could not discriminate images synthesised to match the responses of a mid-level ventral visual stream model when information was averaged in receptive fields with a scaling of about half their retinal eccentricity. This result implicated ventral visual area V2, approximated ‘Bouma’s Law’ of crowding, and has subsequently been interpreted as a link between crowding zones, receptive field scaling, and our perceptual experience. However, this experiment never assessed natural images. We find that humans can easily discriminate real and model-generated images at V2 scaling, requiring scales at least as small as V1 receptive fields to generate metamers. We speculate that explaining why scenes look as they do may require incorporating segmentation and global organisational constraints in addition to local pooling., eLife digest As you read this digest, your eyes move to follow the lines of text. But now try to hold your eyes in one position, while reading the text on either side and below: it soon becomes clear that peripheral vision is not as good as we tend to assume. It is not possible to read text far away from the center of your line of vision, but you can see ‘something’ out of the corner of your eye. You can see that there is text there, even if you cannot read it, and you can see where your screen or page ends. So how does the brain generate peripheral vision, and why does it differ from what you see when you look straight ahead? One idea is that the visual system averages information over areas of the peripheral visual field. This gives rise to texture-like patterns, as opposed to images made up of fine details. Imagine looking at an expanse of foliage, gravel or fur, for example. Your eyes cannot make out the individual leaves, pebbles or hairs. Instead, you perceive an overall pattern in the form of a texture. Our peripheral vision may also consist of such textures, created when the brain averages information over areas of space. Wallis, Funke et al. have now tested this idea using an existing computer model that averages visual input in this way. By giving the model a series of photographs to process, Wallis, Funke et al. obtained images that should in theory simulate peripheral vision. If the model mimics the mechanisms that generate peripheral vision, then healthy volunteers should be unable to distinguish the processed images from the original photographs. But in fact, the participants could easily discriminate the two sets of images. This suggests that the visual system does not solely use textures to represent information in the peripheral visual field. Wallis, Funke et al. propose that other factors, such as how the visual system separates and groups objects, may instead determine what we see in our peripheral vision. This knowledge could ultimately benefit patients with eye diseases such as macular degeneration, a condition that causes loss of vision in the center of the visual field and forces patients to rely on their peripheral vision.

Multidisciplinary team (MDT) diagnosis of interstitial lung disease (ILD) has been proposed as a gold standard, but there are no formal recommendations for MDT process or composition and limited knowledge regarding prevalence in routine practice. We performed a systematic evaluation of ILD diagnostic practice across a range of healthcare settings around the world. Electronic questionnaires were distributed across all global regions via society and collaborators networks. Responses from 457 unique centres across 64 countries were included in the analysis. Of the 350 (76.6%) centres holding formal meetings, the majority held face-to-face MDT meetings (80%), for a minimum of 30 min (93%), and discussed diagnosis (96.9%) and patient management (94.9%) at the meetings. Compared with non-academic and academic non-ILD centres, ILD academic centres reported a higher ILD caseload, held more formal MDT meetings, and were more likely to include histopathology and rheumatology specialists in their diagnostic team. Of the centres holding MDT meetings, 5.5% routinely discussed all new cases at such meetings. An MDT approach to ILD diagnosis is consistently interpreted and widely implemented across a range of routine care settings around the world. This observation will inform future ILD diagnostic agreement studies and diagnostic pathway recommendations. © ERS 2019.

With the rise of machines to human-level performance in complex recognition tasks, a growing amount of work is directed towards comparing information processing in humans and machines. These works have the potential to deepen our understanding of the inner mechanisms of human perception and to improve machine learning. Drawing robust conclusions from comparison studies, however, turns out to be difficult. Here, we highlight common shortcomings that can easily lead to fragile conclusions. First, if a model does achieve high performance on a task similar to humans, its decision-making process is not necessarily human-like. Moreover, further analyses can reveal differences. Second, the performance of neural networks is sensitive to training procedures and architectural details. Thus, generalizing conclusions from specific architectures is difficult. Finally, when comparing humans and machines, equivalent experimental settings are crucial in order to identify innate differences. Addressing these shortcomings alters or refines the conclusions of studies. We show that, despite their ability to solve closed-contour tasks, our neural networks use different decision-making strategies than humans. We further show that there is no fundamental difference between same-different and spatial tasks for common feed-forward neural networks and finally, that neural networks do experience a "recognition gap" on minimal recognizable images. All in all, care has to be taken to not impose our human systematic bias when comparing human and machine perception.

With the rise of machines to human-level performance in complex recognition tasks, a growing amount of work is directed towards comparing information processing in humans and machines. These studies are an exciting chance to learn about one system by studying the other. Here, we propose ideas on how to design, conduct and interpret experiments such that they adequately support the investigation of mechanisms when comparing human and machine perception. We demonstrate and apply these ideas through three case studies. The first case study shows how human bias can affect how we interpret results, and that several analytic tools can help to overcome this human reference point. In the second case study, we highlight the difference between necessary and sufficient mechanisms in visual reasoning tasks. Thereby, we show that contrary to previous suggestions, feedback mechanisms might not be necessary for the tasks in question. The third case study highlights the importance of aligning experimental conditions. We find that a previously-observed difference in object recognition does not hold when adapting the experiment to make conditions more equitable between humans and machines. In presenting a checklist for comparative studies of visual reasoning in humans and machines, we hope to highlight how to overcome potential pitfalls in design or inference., V3: minor changes like in published JOV version (https://doi.org/10.1167/jov.21.3.16) V2: New title; added general section (checklist); manuscript restructured such that each case study is one chapter; adversarial examples in first study replaced by different analysis

We examined how different landscape areas in a catchment containing a northern ombrotrophic peatland and upland mineral soils responded to dramatic decreases in atmospheric deposition of lead (Pb). Pb concentrations in the outflow stream from the peatland measured from 2009-2015 indicated continued mobilization and export of Pb derived from historic inputs to the bog. In contrast, Pb concentrations in surface peat and runoff from upland mineral soils have declined in response to reductions in atmospheric deposition. Relative to the early 1980s, Pb concentrations in the streamflow decreased only ∼50%, while Pb in surface peat and upland subsurface runoff decreased by more than 90%. Water level fluctuations in the slow-accumulating peat have allowed dissolved organic matter (DOM) to continue mobilizing Pb deposited in the peatland decades earlier. Strong correlations between dissolved organic carbon (DOC) and Pb concentrations in outflow from the peatland and in bog porewaters demonstrate Pb mobility related to DOM production. Peat stores of Pb in 2016 were less than or equal to those reported in the early 1980s despite the dry mass inventory increasing by 60-80%. Much of the loss in Pb stored in peat can be accounted for by stream runoff from the peatland.

Electrospinning has emerged as a facile technology for the synthesis of ultrafine fibers and even nanofibers of various materials. While carbon nanofibers have been extensively investigated, there have also been studies reported on metal oxide and metal carbide fibers. Yet, comparative studies, especially following the same general synthesis approach, are lacking. In our comprehensive study, we use a sol gel process by which a carrier polymer (cellulose acetate or polyvinylpyrrolidone) is mixed with titanium butoxide, zirconium(IV) acetylacetonate, or niobium n-butoxide to yield nanotextured titania/carbon, zirconia/carbon, or niobia/carbon nonwoven textiles. Carbothermal reduction between 1300 °C and 1700 °C effectively transforms the metal oxide/carbon fibers to metal carbide/carbon nanocomposite while preserving the fiber integrity. As a beneficial effect, the fiber diameter decreases compared to the as-spun state and we obtained ultrafine fibers: 294 ± 108 nm for ZrC/C, 122 ± 28 nm for TiC/C, and 65 ± 36 nm for NbC/C. The highly disordered and porous nature of the carbon matrix engulfing the metal carbide nanocrystals enables a high specific surface area of up to 450 m2 g−1 (TiC/C) after carbothermal reduction.

Our visual environment is full of texture-"stuff" like cloth, bark, or gravel as distinct from "things" like dresses, trees, or paths-and humans are adept at perceiving subtle variations in material properties. To investigate image features important for texture perception, we psychophysically compare a recent parametric model of texture appearance (convolutional neural network [CNN] model) that uses the features encoded by a deep CNN (VGG-19) with two other models: the venerable Portilla and Simoncelli model and an extension of the CNN model in which the power spectrum is additionally matched. Observers discriminated model-generated textures from original natural textures in a spatial three-alternative oddity paradigm under two viewing conditions: when test patches were briefly presented to the near-periphery ("parafoveal") and when observers were able to make eye movements to all three patches ("inspection"). Under parafoveal viewing, observers were unable to discriminate 10 of 12 original images from CNN model images, and remarkably, the simpler Portilla and Simoncelli model performed slightly better than the CNN model (11 textures). Under foveal inspection, matching CNN features captured appearance substantially better than the Portilla and Simoncelli model (nine compared to four textures), and including the power spectrum improved appearance matching for two of the three remaining textures. None of the models we test here could produce indiscriminable images for one of the 12 textures under the inspection condition. While deep CNN (VGG-19) features can often be used to synthesize textures that humans cannot discriminate from natural textures, there is currently no uniformly best model for all textures and viewing conditions.