Cooperative effects in the oxidation of CO by palladium oxide cations

Cooperative reactivity plays an important role in the oxidation of CO to CO2 by palladium oxide cations and offers insight into factors which influence catalysis. Comprehensive studies including guided-ion-beam mass spectrometry and theoretical investigations reveal the reaction products and profiles of PdO2 + and PdO3 + with CO through oxygen radical centers and dioxygen complexes bound to the Pd atom. O radical centers are more reactive than the dioxygen complexes, and experimental evidence of both direct and cooperative CO oxidation with the adsorption of two CO molecules are observed. The binding of multiple electron withdrawing CO molecules is found to increase the barrier heights for reactivity due to decreased binding of the secondary CO molecule, however, reactivity is enhanced by the increase in kinetic energy available to hurdle the barrier. We examine the effect of oxygen sites, cooperative ligands, and spin including two-state reactivity

Carbon concentration of standing and downed woody detritus: Effects of tree taxa, decay class, position, and tissue type

The degree to which carbon concentration (CC) of woody detritus varies by tree taxa, stage of decay, tissue type (i.e., bark versus wood), and vertical orientation was examined in samples of 60 tree species from the Northern Hemisphere. The mean CC of 257 study samples was 49.3% with a range of 43.4– 56.8%. Angiosperms had a significantly lower CC than gymnosperms, with means of 47.8% and 50.6%, respectively. For whole-stems (i.e., wood and bark), the CC of gymnosperms significantly increased from 49.3% to 53.5% with decomposition, while angiosperms had no significant change. The CC of bark was higher than wood across all stages of decay by an average of ~1.0%. A similar magnitude of difference was found for standing versus downed dead wood in the later stages of decay, with the former having a higher CC than the latter. Differences between angiosperms and gymnosperms are hypothesized to be associated with initial lignin concentrations as well as subsequent decomposition by white- versus brown-rot fungal functional groups. The higher abundance of brown-rots in decomposing gymnosperms may lead to an increase in lignin concentrations, a compound that has higher CC than cellulose. As a result of these findings, uncertainties associated with forest carbon inventories may be reduced by using detrital CC specific to general taxa (angiosperms versus gymnosperms) and stage of decay rather than a single assumed value of 50% as commonly practiced.Keywords: Carbon, Gymnosperm, Bark, Coarse woody debris, Angiosperm, Woo

Enhancement of Surfactants in Nanoparticles Produced by an Electrospray Aerosol Generator

Electrospray aerosol generators (EAGs) disperse conducting solutions into air, promptly neutralize the particles to remove the excess charge, and evaporate the residual solvent with a dry air flow. For solutions containing multiple solutes, the particles may become enhanced in the more surface-active solutes. The extent of the enhancement was estimated for nanoparticles electrosprayed from a solution containing NaCl and surfactant sodium dodecyl sulfate (SDS) mixed in a 9:1 weight ratio. A tandem particle mobility analyzer was used to quantify the hygroscopic growth factor (GF). The relative fractions of NaCl and SDS in the particles were estimated from the measured GFs assuming that NaCl and SDS take up water independently of each other. The nanoparticles were considerably enhanced in SDS relative to the starting solution, with the NaCl:SDS weight ratio increasing with the distance from the EAG electrified capillary tip to the neutralizer, and reaching ∼1:1 at the longest distances probed. The enhancement in SDS likely occurred during particle fission events as particles traveled from the capillary to the neutralizer. This study has practical ramifications for aerosol nanotechnology and aerosol-assisted drug delivery, which rely on EAG as an instrument of choice for nanoparticle generation

Impact of Prolonged Professional Development on Teachers’ Confidence in Using Inquiry-Based Learning in the Classroom

Professional development (PD) programs for science and agriculture teachers designed around the inquiry-based learning (IBL) teaching strategy could help to improve science proficiency amongst our high school students. PD that continues over a longer period of time is more effective than short-term workshops. The purpose of this study was to explore the impact of a prolonged PD program on teachers’ confidence in using IBL strategies for teaching animal sciences content. The following research questions guided this study: RQ1: What were participants’ perceptions of a prolonged PD program? and RQ2: How did the prolonged PD program influence the participants’ confidence in using IBL? For this project, the teachers completed three online modules focused on best practices for using IBL in the classroom and then participated in a five-day in-person PD program that was offered in Tennessee and Nebraska during June and July of 2022. Basic qualitative methodology was used, and four focus groups were conducted. The following themes emerged: perceptions of the PD and confidence in using IBL. Allowing teachers to work through the IBL activities as students appeared to increase their confidence in using IBL to teach animal science concepts in the future

Real-world outcomes of sipuleucel-T treatment in PROCEED, a prospective registry of men with metastatic castration-resistant prostate cancer.

BackgroundThe large registry, PROVENGE Registry for the Observation, Collection, and Evaluation of Experience Data (PROCEED)(NCT01306890), evaluated sipuleucel-T immunotherapy for asymptomatic/minimally symptomatic metastatic castration-resistant prostate cancer (mCRPC).MethodsPROCEED enrolled patients with mCRPC receiving 3 biweekly sipuleucel-T infusions. Assessments included overall survival (OS), serious adverse events (SAEs), cerebrovascular events (CVEs), and anticancer interventions (ACIs). Follow-up was for ≥3 years or until death or study withdrawal.ResultsIn 2011-2017, 1976 patients were followed for 46.6 months (median). The median age was 72 years, and the baseline median prostate-specific antigen level was 15.0 ng/mL; 86.7% were white, and 11.6% were African American. Among the patients, 1902 had 1 or more sipuleucel-T infusions. The median OS was 30.7 months (95% confidence interval [CI], 28.6-32.2 months). Known prognostic factors were independently associated with OS in a multivariable analysis. Among the 1255 patients who died, 964 (76.8%) died of prostate cancer (PC) progression. The median time from the first infusion to PC death was 42.7 months (95% CI, 39.4-46.2 months). The incidence of sipuleucel-T-related SAEs was 3.9%. The incidence of CVEs was 2.8%, and the rate per 100 person-years was 1.2 (95% CI, 0.9-1.6). The CVE incidence among 11,972 patients with mCRPC from the Surveillance, Epidemiology, and End Results-Medicare database was 2.8%; the rate per 100 person-years was 1.5 (95% CI, 1.4-1.7). One or more ACIs (abiraterone, enzalutamide, docetaxel, cabazitaxel, or radium 223) were received by 77.1% of the patients after sipuleucel-T; 32.5% and 17.4% of the patients experienced 1- and 2-year treatment-free intervals, respectively.ConclusionsPROCEED provides contemporary survival data for sipuleucel-T-treated men in a real-world setting of new life-prolonging agents, which will be useful in discussing treatment options with patients and in powering future trials with sipuleucel-T. The safety and tolerability of sipuleucel-T in PROCEED were consistent with previous findings

Climatic regions as an indicator of forest coarse and fine woody debris carbon stocks in the United States

<p>Abstract</p> <p>Background</p> <p>Coarse and fine woody debris are substantial forest ecosystem carbon stocks; however, there is a lack of understanding how these detrital carbon stocks vary across forested landscapes. Because forest woody detritus production and decay rates may partially depend on climatic conditions, the accumulation of coarse and fine woody debris carbon stocks in forests may be correlated with climate. This study used a nationwide inventory of coarse and fine woody debris in the United States to examine how these carbon stocks vary by climatic regions and variables.</p> <p>Results</p> <p>Mean coarse and fine woody debris forest carbon stocks vary by Köppen's climatic regions across the United States. The highest carbon stocks were found in regions with cool summers while the lowest carbon stocks were found in arid desert/steppes or temperate humid regions. Coarse and fine woody debris carbon stocks were found to be positively correlated with available moisture and negatively correlated with maximum temperature.</p> <p>Conclusion</p> <p>It was concluded with only medium confidence that coarse and fine woody debris carbon stocks may be at risk of becoming net emitter of carbon under a global climate warming scenario as increases in coarse or fine woody debris production (sinks) may be more than offset by increases in forest woody detritus decay rates (emission). Given the preliminary results of this study and the rather tenuous status of coarse and fine woody debris carbon stocks as either a source or sink of CO₂, further research is suggested in the areas of forest detritus decay and production.</p

Accounting for density reduction and structural loss in standing dead trees: Implications for forest biomass and carbon stock estimates in the United States

<p>Abstract</p> <p>Background</p> <p>Standing dead trees are one component of forest ecosystem dead wood carbon (C) pools, whose national stock is estimated by the U.S. as required by the United Nations Framework Convention on Climate Change. Historically, standing dead tree C has been estimated as a function of live tree growing stock volume in the U.S.'s National Greenhouse Gas Inventory. Initiated in 1998, the USDA Forest Service's Forest Inventory and Analysis program (responsible for compiling the Nation's forest C estimates) began consistent nationwide sampling of standing dead trees, which may now supplant previous purely model-based approaches to standing dead biomass and C stock estimation. A substantial hurdle to estimating standing dead tree biomass and C attributes is that traditional estimation procedures are based on merchantability paradigms that may not reflect density reductions or structural loss due to decomposition common in standing dead trees. The goal of this study was to incorporate standing dead tree adjustments into the current estimation procedures and assess how biomass and C stocks change at multiple spatial scales.</p> <p>Results</p> <p>Accounting for decay and structural loss in standing dead trees significantly decreased tree- and plot-level C stock estimates (and subsequent C stocks) by decay class and tree component. At a regional scale, incorporating adjustment factors decreased standing dead quaking aspen biomass estimates by almost 50 percent in the Lake States and Douglas-fir estimates by more than 36 percent in the Pacific Northwest.</p> <p>Conclusions</p> <p>Substantial overestimates of standing dead tree biomass and C stocks occur when one does not account for density reductions or structural loss. Forest inventory estimation procedures that are descended from merchantability standards may need to be revised toward a more holistic approach to determining standing dead tree biomass and C attributes (i.e., attributes of tree biomass outside of sawlog portions). Incorporating density reductions and structural loss adjustments reduces uncertainty associated with standing dead tree biomass and C while improving consistency with field methods and documentation.</p

Interactions between white-tailed deer density and the composition of forest understories in the northern United States

Forest understories across the northern United States (US) are a complex of tree seedlings, endemic forbs, herbs, shrubs, and introduced plant species within a forest structure defined by tree and forest floor attributes. The substantial increase in white-tailed deer (Odocoileus virginianus Zimmerman) populations over the past decades has resulted in heavy browse pressure in many of these forests. To gain an objective assessment of the role of deer in forested ecosystems, a region-wide forest inventory across the northern US was examined in concert with white-tailed deer density information compiled at broad scales. Results indicate that deer density may be an additional driver of tree seedling abundance when analyzed along with stand attributes such as above ground biomass, relative density, and stand age. Tree seedling abundance generally decreased as deer density increased above 5.8 deer km2 for all forest type groups with the exception of oak-dominated forests. Findings indicate that introduced plant species, of which 393 were recorded in this study, increased in areas with higher deer density. The abundance of white-tailed deer is just as important as forest stand and site attributes in the development of forest understories. Given the complexity of forest and land use dynamics across the northern US, this study provides directions for future research as more data linking forest-dependent wildlife and forest dynamics at regional and national scales become available

Finding Our Way through Phenotypes

Despite a large and multifaceted effort to understand the vast landscape of phenotypic data, their current form inhibits productive data analysis. The lack of a community-wide, consensus-based, human- and machine-interpretable language for describing phenotypes and their genomic and environmental contexts is perhaps the most pressing scientific bottleneck to integration across many key fields in biology, including genomics, systems biology, development, medicine, evolution, ecology, and systematics. Here we survey the current phenomics landscape, including data resources and handling, and the progress that has been made to accurately capture relevant data descriptions for phenotypes. We present an example of the kind of integration across domains that computable phenotypes would enable, and we call upon the broader biology community, publishers, and relevant funding agencies to support efforts to surmount today's data barriers and facilitate analytical reproducibility