Converting CO2 into value-added chemicals and fuels, such as methanol, is a promising approach to limit the environmental impact of human activities. Conventional methanol synthesis catalysts have ...shown limited efficiency and poor stability in a CO2/H2 mixture. To design improved catalysts, crucial for the effective utilization of CO2, an in-depth understanding of the active sites and reaction mechanism is desired. The catalytic performance of a series of carbon-supported Cu catalysts, with Cu particle sizes in the range of 5 to 20 nm, was evaluated under industrially relevant temperature and pressure, i.e. 260 °C and 40 bar(g). The CO2 hydrogenation reaction exhibited clear particle size effects up to 13 nm particles, with small nanoparticles having the lower activity, but higher methanol selectivity. MeOH and CO formation showed a different size-dependence. The TOFCO increased from 1.9 × 10−3 s−1 to 9.4 × 10−3 s−1 with Cu size increasing from 5 nm to 20 nm, while the TOFMeOH was size-independent (8.4 × 10−4 s−1 on average). The apparent activation energies for MeOH and CO formation were size-independent with values of 63 ± 7 kJ mol−1 and 118 ± 6 kJ mol−1, respectively. Hence the size dependence was ascribed to a decrease in the fraction of active sites suitable for CO formation with decreasing particle size. Theoretical models and DFT calculations showed that the origin of the particle size effect is most likely related to the differences in formate coverage for different Cu facets whose abundancy depends on particle size. Hence, the CO2 hydrogenation reaction is intrinsically sensitive to the Cu particle size.
Research suggests that an emphasis on spirituality and religion in counseling has increased awareness but not translated into changes in practice. The authors contend that part of this challenge is ...the lack of a broad, heuristic model for integration that seeks to embrace the complex, fluid, and negotiated nature of spirituality and religion. Cheston's () Ways Paradigm for teaching counseling theory provides such a model, leading to new perspectives on counselor education, research, and practice.
Aim: The American pika (Ochotona princeps) appears to have experienced climatemediated upslope range contraction in the Great Basin of North America, but this result has not yet been extended to ...other portions of the pika's range. Our goals were: first, to determine the environmental parameters that most influence current pika distribution within California; second, to infer whether these constraints explain extirpations that have occurred in California; third, to predict future extirpations; and fourth, to advance methods for assessing the degree to which pikas and other climate-sensitive mammals are threatened by climate change. Location: Historical pika record locations in California, USA, spanning four degrees of latitude and longitude, from Mount Shasta to the southern Sierra Nevada. Methods: We identified 67 precise historical pika record locations and surveyed them exhaustively, over multiple years, to determine whether pika populations persist at those sites. We used an information theoretic approach and logistic regression to model current pika occupancy as a function of 16 environmental variables, tested our best-performing model as a predictor of historical occupancy, and then used our model to predict future pika occupancy given anticipated climate change. Results: Pikas no longer occurred at 10 of 67 (15%) historical sites in California. The best predictors of occupancy were average summer temperature and talus habitat area within a 1-km radius. A logistic model fitted to this relationship correctly predicted current occupancy at 94% of sites and correctly hindcasted past occupancy at 93% of sites, suggesting that the model has strong temporal transferability. Depending on the future climate scenario, our model projects that by 2070 pikas will be extirpated from 39% to 88% of these historical sites in California. Main conclusions: Our simple species distribution model for pikas performs remarkably well for both current and historical periods. Pika distribution appears to be governed primarily by behavioural restrictions mediated by summer temperature and by the configuration of talus habitat available to pikas locally. Pikas, and other montane species in the western USA, may be subjected to above-average exposure to climate change because summer temperature is projected to rise more than annual temperature.
Progressive Supranuclear Palsy (PSP) is the most common atypical parkinsonism and exhibits hallmark symptomology including motor function impairment and dysexecutive dementia. In contrast to ...Parkinson's disease, the underlying pathology displays aggregation of the protein tau, which is also seen in disorders such as Alzheimer's disease. Currently, there are no pharmacological treatments for PSP, and drug discovery efforts are hindered by the lack of an animal model specific to PSP. Based on previous results and clinical pathology, it was hypothesized that viral deposition of tau in cholinergic neurons within the hindbrain would produce a tauopathy along neural connections to produce PSP‐like symptomology and pathology. By using a combination of ChAT‐CRE rats and CRE‐dependent AAV vectors, wildtype human tau (the PSP‐relevant 1N4R isoform; hTau) was expressed in hindbrain cholinergic neurons. Compared to control subjects (GFP), rats with tau expression displayed deficits in a variety of behavioural paradigms: acoustic startle reflex, marble burying, horizontal ladder and hindlimb motor reflex. Postmortem, the hTau rats had significantly reduced number of cholinergic pedunculopontine tegmentum and dopaminergic substantia nigra neurons, as well as abnormal tau deposits. This preclinical model has multiple points of convergence with the clinical features of PSP, some of which distinguish between PSP and Parkinson's disease.
Cre‐dependent AAV constructs expressing either GFP or hTau was injected into the PPT of ChAT‐CRE rats (A‐B). Within weeks, the hTau expressing group showed significant behavioural deficits (C; motor—horizontal ladder) and tau pathology (D; AT8) that are consistent with PSP.
Understanding nanoparticle growth is crucial to increase the lifetime of supported metal catalysts. In this study, we employ in situ gas-phase transmission electron microscopy to visualize the ...movement and growth of ensembles of tens of nickel nanoparticles supported on carbon for CO2 hydrogenation at atmospheric pressure (H2:CO2 = 4:1) and relevant temperature (450 °C) in real time. We observe two modes of particle movement with an order of magnitude difference in velocity: fast, intermittent movement (v max = 0.7 nm s–1) and slow, gradual movement (v average = 0.05 nm s–1). We visualize the two distinct particle growth mechanisms: diffusion and coalescence, and Ostwald ripening. The diffusion and coalescence mechanism dominates at small interparticle distances, whereas Ostwald ripening is driven by differences in particle size. Strikingly, we demonstrate an interplay between the two mechanisms, where first coalescence takes place, followed by fast Ostwald ripening due to the increased difference in particle size. Our direct visualization of the complex nanoparticle growth mechanisms highlights the relevance of studying nanoparticle growth in supported nanoparticle ensembles under reaction conditions and contributes to the fundamental understanding of the stability in supported metal catalysts.
Background Nurses are frequently interrupted during medication verification and administration; however, few interventions exist to mitigate resulting errors, and the impact of these interventions on ...medication safety is poorly understood. Objective The study objectives were to (A) assess the effects of interruptions on medication verification and administration errors, and (B) design and test the effectiveness of targeted interventions at reducing these errors. Methods The study focused on medication verification and administration in an ambulatory chemotherapy setting. A simulation laboratory experiment was conducted to determine interruption-related error rates during specific medication verification and administration tasks. Interventions to reduce these errors were developed through a participatory design process, and their error reduction effectiveness was assessed through a postintervention experiment. Results Significantly more nurses committed medication errors when interrupted than when uninterrupted. With use of interventions when interrupted, significantly fewer nurses made errors in verifying medication volumes contained in syringes (16/18; 89% preintervention error rate vs 11/19; 58% postintervention error rate; p=0.038; Fisher's exact test) and programmed in ambulatory pumps (17/18; 94% preintervention vs 11/19; 58% postintervention; p=0.012). The rate of error commission significantly decreased with use of interventions when interrupted during intravenous push (16/18; 89% preintervention vs 6/19; 32% postintervention; p=0.017) and pump programming (7/18; 39% preintervention vs 1/19; 5% postintervention; p=0.017). No statistically significant differences were observed for other medication verification tasks. Conclusions Interruptions can lead to medication verification and administration errors. Interventions were highly effective at reducing unanticipated errors of commission in medication administration tasks, but showed mixed effectiveness at reducing predictable errors of detection in medication verification tasks. These findings can be generalised and adapted to mitigate interruption-related errors in other settings where medication verification and administration are required.
Long-tract gene conversions (LTGC) can result from the repair of collapsed replication forks, and several mechanisms have been proposed to explain how the repair process produces this outcome. We ...studied LTGC events produced from repair collapsed forks at yeast fragile site FS2. Our analysis included chromosome sizing by contour-clamped homogeneous electric field electrophoresis, next-generation whole-genome sequencing, and Sanger sequencing across repair event junctions. We compared the sequence and structure of LTGC events in our cells to the expected qualities of LTGC events generated by proposed mechanisms. Our evidence indicates that some LTGC events arise from half-crossover during BIR, some LTGC events arise from gap repair, and some LTGC events can be explained by either gap repair or "late" template switch during BIR. Also based on our data, we propose that models of collapsed replication forks be revised to show not a one-end double-strand break (DSB), but rather a two-end DSB in which the ends are separated in time and subject to gap repair.
This study investigates the conditions for which one-dimensional (1-D) nonlinear (NL) site response analysis results are distinct from equivalent-linear (EL) results and provides guidance for ...predicting when differences are large enough to be of practical significance. Relative differences in spectral accelerations and Fourier amplitudes computed from NL and EL analyses are assessed for a range of site conditions and for suites of input motions appropriate for active crustal and stable continental regions. Among several considered parameters, EL/NL differences are most clearly dependent on shear strain index (Iγ), defined as the ratio of input motion peak velocity to time-averaged shear-wave velocity in the top 30 m of the soil profile. For small Iγ (generally under 0.03%), EL and NL results are practically identical, whereas at larger strains, differences can be significant for frequencies >0.3 Hz. Frequency-dependent Iγ values are recommended for conditions above which NL analyses are preferred to EL.
Changes in both silicate weathering rates and organic carbon burial have been proposed as drivers of the transient “Mi‐1” glaciation event at the Oligocene‐Miocene transition (OMT; ~23 Ma). However, ...detailed geochemical proxy data are required to test these hypotheses. Here we present records of Li/Ca, Mg/Ca, Cd/Ca, U/Ca, δ18O, δ13C, and shell weight in planktonic foraminifera from marine sediments spanning the OMT in the equatorial Atlantic Ocean. Li/Ca values increase by 1 μmol/mol across this interval. We interpret this to indicate an ~20% increase in silicate weathering rates, which would have lowered atmospheric CO2, potentially forcing the Antarctic glaciation ~ 23 Ma. δ13C of thermocline dwelling planktonic foraminifera track the global increase in seawater δ13C across the OMT and during the Mi‐1 event, hence supporting a hypothesized global increase in organic carbon burial rates. High δ13C previously measured in epipelagic planktonic foraminifera and high Cd/Ca ratios during Mi‐1 are interpreted to represent locally enhanced primary productivity, stimulated by increased nutrients supply to surface waters. The fingerprint of high export production and associated organic carbon burial at this site is found in reduced bottom water oxygenation (inferred from high foraminiferal U/Ca) and enhanced respiratory dissolution of carbonates, characterized by reduced foraminiferal shell weight. Replication of our results elsewhere would strengthen the case that weathering‐induced CO2 sequestration preconditioned climate for Antarctic ice sheet growth across the OMT, and increased burial of organic carbon acted as a feedback that intensified cooling at this time.
Key Points
Foraminiferal Li/Ca suggests that silicate weathering rates increased across the O/M boundary
High δ13C and Cd/Ca during Mi‐1 indicate increased primary productivity and nutrient availability
High U/Ca and low shell weight during Mi‐1 suggest increased organic carbon burial
Using DNA methylation profiles (
= 15,456) from 348 mammalian species, we constructed phyloepigenetic trees that bear marked similarities to traditional phylogenetic ones. Using unsupervised ...clustering across all samples, we identified 55 distinct cytosine modules, of which 30 are related to traits such as maximum life span, adult weight, age, sex, and human mortality risk. Maximum life span is associated with methylation levels in
subclass homeobox genes and developmental processes and is potentially regulated by pluripotency transcription factors. The methylation state of some modules responds to perturbations such as caloric restriction, ablation of growth hormone receptors, consumption of high-fat diets, and expression of Yamanaka factors. This study reveals an intertwined evolution of the genome and epigenome that mediates the biological characteristics and traits of different mammalian species.