Role of Fe decoration on the oxygen evolving state of Co3O4 nanocatalysts.

The production of green hydrogen through alkaline water electrolysis is the key technology for the future carbon-neutral industry. Nanocrystalline Co3O4 catalysts are highly promising electrocatalysts for the oxygen evolution reaction and their activity strongly benefits from Fe surface decoration. However, limited knowledge of decisive catalyst motifs at the atomic level during oxygen evolution prevents their knowledge-driven optimization. Here, we employ a variety of operando spectroscopic methods to unveil how Fe decoration increases the catalytic activity of Co3O4 nanocatalysts as well as steer the (near-surface) active state formation. Our study shows a link of the termination-dependent Fe decoration to the activity enhancement and a significantly stronger Co3O4 near-surface (structural) adaptation under the reaction conditions. The near-surface Fe- and Co-O species accumulate an oxidative charge and undergo a reversible bond contraction during the catalytic process. Moreover, our work demonstrates the importance of low coordination surface sites on the Co3O4 host to ensure an efficient Fe-induced activity enhancement, providing another puzzle piece to facilitate optimized catalyst design.

Operando insights into correlating CO coverage and Cu-Au alloying with the selectivity of Au NP-decorated Cu2O nanocubes during the electrocatalytic CO2 reduction.

Electrochemical reduction of CO2 (CO2RR) is an attractive technology to reintegrate the anthropogenic CO2 back into the carbon cycle driven by a suitable catalyst. This study employs highly efficient multi-carbon (C2+) producing Cu2O nanocubes (NCs) decorated with CO-selective Au nanoparticles (NPs) to investigate the correlation between a high CO surface concentration microenvironment and the catalytic performance. Structure, morphology and near-surface composition are studied via operando X-ray absorption spectroscopy and surface-enhanced Raman spectroscopy, operando high-energy X-ray diffraction as well as quasi in situ X-ray photoelectron spectroscopy. These operando studies show the continuous evolution of the local structure and chemical environment of our catalysts during reaction conditions. Along with its alloy formation, a CO-rich microenvironment as well as weakened average CO binding on the catalyst surface during CO2RR is detected. Linking these findings to the catalytic function, a complex compositional interplay between Au and Cu is revealed in which higher Au loadings primarily facilitate CO formation. Nonetheless, the strongest improvement in C2+ formation appears for the lowest Au loadings, suggesting a beneficial role of the Au-Cu atomic interaction for the catalytic function in CO2RR. This study highlights the importance of site engineering and operando investigations to unveil the electrocatalyst's adaptations to the reaction conditions, which is a prerequisite to understand its catalytic behavior.

Evaluation of oncology infusion pharmacy practices: A nationwide survey.

PURPOSE: Oncology care continues to evolve at a rapid pace including provision of infusion-based care. There is currently a lack of robust metrics around oncology infusion centers and pharmacy practice. The workgroup completed a nationwide survey to learn about oncology-based infusion pharmacy services offered. The objective was to highlight consistent, measureable oncology-based infusion pharmacy metrics that will provide a foundation to describe overall productivity including emphasis on high patient-safety standards. METHODS: A nationwide survey was developed via a workgroup within the Vizient Pharmacy Cancer Care Group beginning in April 2019 and conducted electronically via the Vizient Pharmacy Network from September to November 2020. The survey was designed to capture a number of key metrics related to oncology-based infusion pharmacy services. RESULTS: Forty-one sites responded to the survey. Responses highlighted hours of operation (median = 11.5), number of infusion chairs (median = 45). Staffing metrics included 7.1 pharmacist full-time equivalent (FTE) and 7.6 technician FTE per week. 80.5% of sites had cleanrooms and 95.1% reported both hazardous and nonhazardous compounding hoods. 68.3% of sites reported using intravenous (IV) technology, 50.0% measured turnaround time, and 31.4% prepared treatment medications in advance. CONCLUSION: There was variability among oncology infusion pharmacy practices in regard to survey responses among sites. The survey results highlight the need for standardization of established productivity metrics across oncology infusion pharmacies in order to improve efficiency and contain costs in the changing oncology landscape. The survey provides insight into oncology infusion pharmacy practices nationwide and provides information for pharmacy leaders to help guide their practices.

Post hoc experimental designs improve genetic trial analyses: A case study of cherrybark oak (Quercus pagoda Raf.) genetic evaluation in the western Gulf region, USA.

Oaks (Quercus spp.) are widespread hardwood trees in the Northern Hemisphere and of high ecological, economic, and social values. Optimal experimental design of genetic trials is essential for accurate estimates of genetic parameters and improving the genetic merit of breeding stock. Here, we evaluate the use of post hoc row-column factors combined with spatial adjustment to improve genetic analyses of parents and individual trees in field progeny tests of plantation hardwoods, using cherrybark oak (Quercus pagoda Raf.) as an example. For tree height, post hoc incomplete blocking reduced ~14% more of the within-block environmental variance compared to the randomized complete block design (RCBD) model. Incomplete blocking also improved the heritability estimates for height by 7% to 14% compared to the original RCBD model. No clinal trend for growth breeding values was identified due to provenances. Our approach warrants the initial selection for height as early as age ~10 based on its moderate narrow-sense heritability of 0.2; however, diameter and volume need longer evaluation times. The post hoc incomplete blocking is more efficient and promising to improve the genetic analysis of Q. pagoda to minimize the environmental heterogeneity influences. Adjusting competition and spatial effects, including the distance principal components and autoregressive residual structure notably improves the model fit based on the observed reductions in AICs and BICs. Employing our approach is promising for hardwood genetic improvement in the southern USA.

Healthcare workers benefit from second dose of COVID-19 mRNA vaccine: Effects of partial and full vaccination on sick leave duration and symptoms

ImportanceIn addition to morbidity and mortality of individuals, COVID-19 can affect staffing among organizations. It is important to determine whether vaccination can mitigate this burden. Objective: This study examined the association between COVID-19 vaccination status and time until return to work among 952 healthcare workers (HCW) who tested positive for COVID-19. DesignData were collected prospectively between December 2020 and July 2021. HCW who tested positive for COVID-19 completed an initial interview and were followed until they returned to work. SettingAn academic campus in Southern California consisting of two large hospitals and multiple outpatient clinics and other facilities. ParticipantsClinical and nonclinical HCW who tested positive for COVID-19 during the study period (N=952, mean age=39.2 years, 69% female, 45% Hispanic, 14% white, 14% Asian/Pacific Islander, 5% African American, and 21% other race/ethnicity). ExposureCOVID-19 vaccination status (unvaccinated, partially vaccinated, or fully vaccinated) Main Outcome MeasuresDays until return to work, presenting symptom ResultsReturn-to-work time for fully vaccinated HCWs (mean=10.9 days) was significantly shorter than that of partially vaccinated HCWs (15.5 days), which in turn was significantly shorter than that of unvaccinated HCWs (18.0 days). Fully vaccinated HCWs also showed milder symptom profiles compared to partially vaccinated and unvaccinated HCWs. Conclusions and RelevanceCOVID-19 vaccination has the potential to prevent long absences from work and the adverse financial, staffing, and managerial consequences of these long absences. KEY POINTSO_ST_ABSQuestionC_ST_ABSDo healthcare workers (HCW) who are vaccinated against COVID-19 return to work sooner and experience milder symptoms compared with unvaccinated HCW? FindingsAmong 952 healthcare workers who tested positive for COVID-19 between December 2020 and July 2021, return-to-work time for fully vaccinated HCWs (mean=10.9 days) was significantly shorter than that of partially vaccinated HCWs (15.5 days), which in turn was significantly shorter than that of unvaccinated HCWs (18.0 days). Fully vaccinated HCWs also showed milder symptom profiles compared to partially vaccinated and unvaccinated HCWs. MeaningCOVID-19 vaccination has the potential to prevent long absences from work and the adverse financial, staffing, and managerial consequences of these long absences.

Surface core level BE shifts for CaO(100): insights into physical origins.

The relationship between the electronic structure of CaO and the binding energy, BE, shifts between surface and bulk atoms is examined and the physical origins of these shifts are established. Furthermore, the contribution of covalent mixing to the interaction, including the energetic importance, is investigated and found to be small. In particular, the small shift between surface and bulk O(1s) BEs is shown to originate from changes in the polarizable charge distribution of surface O anions. This relationship, which is relevant for the catalytic properties of CaO, follows because the BE shifts are dominated by initial state contributions and the relaxation in response to the core-ionization is similar for bulk and surface. In order to explain the dominance of initial state effects for the BE shifts, the relaxation is decomposed into atomic and extra-atomic contributions. The bonding and the core-level BE shifts have been studied using cluster models of CaO with Hartree-Fock wavefunctions. The theoretical shifts are compared with X-ray photoelectron spectroscopy measurements where both angular resolution and incident photon energy have been used to distinguish surface and bulk ionization.

Deaminative Arylation of Amino Acid-derived Pyridinium Salts.

A Suzuki-Miyaura cross-coupling of α-pyridinium esters and arylboroxines has been developed. Combined with formation of the pyridinium salts from amino acid derivatives, this method enables amino acid derivatives to be efficiently transformed into α-aryl esters and amides. Under the mild conditions, broad functional group tolerance on both the amino acid derivatives and the arylboroxine are observed, including protic functional groups. Mechanistic studies support an alkyl radical intermediate, similar to other cross-couplings of alkylpyridinium salts.

Diagnostic Approaches to Understanding Equine Limb Wounds.

An accurate and timely diagnosis of the systemic and local tissue influences of a wound are essential to target successful treatment measures and reach the best result for an affected horse. A complete physical examination should be completed for any wounded horse and appropriate systemic therapies instituted. Visual and manipulative examinations aid in the complete understanding of wounded tissues. Imaging and invasive diagnostic techniques also have value in determining the extent of a wound. Considering what tissues are involved from an inside-out perspective can assist in developing a complete diagnosis.

Flexural Limb Deformities of the Carpus and Fetlock in Foals.

Early recognition and treatment of congenital and acquired flexural deformities of the carpi and fetlocks of foals can lead to conformation correction and an athletic future. Treatment is often based on rigid external coaptation assisted by systemic medical treatment. Foals that readily respond to treatment and correct conformation faults can have normal adult athletic expectations.

Outcomes after autologous SCT in lymphoma patients grouped by weight.

Obesity continues to be an increasing global health issue contributing to the complexity of chemotherapy dosing in the field of SCT. Investigation into the optimal dosing weight used to calculate chemotherapy doses in obese patients undergoing SCT is limited and inconclusive. Our single-center, retrospective study compared safety and efficacy outcomes by body mass index (BMI) for 476 adult lymphoma patients who underwent auto-SCT with a myeloablative chemotherapeutic regimen of BU, CY and etoposide dosed using adjusted body weight. Three weight groups categorized based on BMI were defined: normal/underweight ⩽24.9 kg/m(2), overweight 25-29.9 kg/m(2) and obese ⩾30 kg/m(2). Severity of mucositis, incidence of secondary malignancy, incidence of bacteremia and median hospital length of stay did not differ among the groups. The median times to absolute neutrophil count and platelet recovery were 10 days (P=0.75) and 14 days (P=0.17), respectively. Obese patients had a lower 100-day mortality compared with other weight groups, although this did not translate into an OS benefit. OS and disease relapse were similar among the groups. Our study demonstrates that use of adjusted body weight to calculate chemotherapy doses does not negatively have an impact on outcomes in obese patients undergoing auto-SCT with BU, CY and etoposide.

Histiocytic necrotising lymphadenitis (Kikuchi-Fujimoto disease) of axillary lymph nodes.

Kikuchi-Fujimoto disease (KFD) or histiocytic necrotising lymphadenitis is a rare entity, occurring most commonly in young Asian adults. KFD is characterised by fever with tender lymph node enlargement. The cervical group of lymph nodes is most commonly involved, and the diagnosis is conclusively made by lymph node biopsy and histopathology. KFD is a self-limiting condition, which usually resolves over 1-4 months. Symptomatic treatment with antipyretics and/or non-steroidal anti-inflammatory drugs is recommended. Here we describe an uncommon presentation of KFD in a young woman in which only the axillary lymph nodes were enlarged.

The uefa euro 2012 anti-doping programme - scientific review.

The final tournament of the UEFA European Football Championship is one of the top sporting events in the world, and a high-profile event of this kind requires a well-planned and well-executed anti-doping programme to ensure the integrity of results in the competition. UEFA EURO 2012 presented a unique logistical challenge, with the tournament spread across two countries, both covering a large geographical area. This paper discusses the planning and delivery of both the pre tournament out-of-competition (OOC) testing programme and the in-competition (IC) programme, as well as reviewing the activities of doping control officers (DCOs), the whereabouts programme and assessing the sample collection and transport process. The analytical approach applied is also discussed, along with an overview of the distribution of T/E ratios and blood parameters.

The application of hyperbaric oxygen therapy in the management of compromised flaps.

INTRODUCTION: Hyperbaric oxygen (HBO2) therapy has been used to promote viability of compromised flaps despite a paucity of supportive clinical evidence. This study provides an in-depth characterization of hyperbaric medicine to promote flap survival and identifies treatment variables associated with positive clinical outcomes. METHODS: A retrospective review was conducted of patients who received HBO2 therapy for a failing or threatened post-reconstructive flap from 5/30/2008 through 4/30/2012. Medical records were reviewed to collect patient characteristics, hyperbaric oxygen therapy details, and clinical outcomes. Descriptive and comparative statistics were utilized. RESULTS: Ninety-one patients underwent HBO2 therapy during this time period, with 15 patients meeting the selection criteria. Flap survival was achieved in 11 patients (73.3%). Of those successfully treated, four (36.4%) healed completely, and seven (63.6%) demonstrated marked improvement. Patients who were treated successfully demonstrated an average improvement in flap area of 68.3%. Variables significantly associated with a favorable treatment outcome included a high percentage of treatment completion (p = 0.022) and high pretreatment transcutaneous oxygen measurements (p = 0.05). Smoking was a negative factor (p = 0.011). CONCLUSION: This study provides clinical data characterizing and supporting the application of hyperbaric medicine to aid in the viability of compromised flaps.

Ultrasonographic visualization of colonic mesenteric vasculature as an indicator of large colon right dorsal displacement or 180° volvulus (or both) in horses.

Visualization of colonic mesenteric vasculature during transabdominal ultrasonographic examination of horses with colic can be a predictor of right dorsal displacement of the large colon or 180° large colon volvulus, or both. Medical records of 82 horses having had surgical treatment of colic and having received a transabdominal ultrasonographic examination on admission were reviewed. Colonic mesenteric vessels were sonographically identified coursing laterally on the right side of the abdomen in 24 of the 82 cases. Horses with colonic vessels identified on ultrasound were 32.5 times more likely to be diagnosed at surgery with either large colon right dorsal displacement or 180° large colon volvulus than those in which vessels were not seen (P < 0.001). Visualization of colonic mesenteric vessels on ultrasound provided a sensitivity of 67.7%, specificity of 97.9%, positive predictive value of 95.8%, and negative predictive value of 81% for large colon right dorsal displacement or 180° large colon volvulus, or both.

Case report: squamous cell carcinoma of the urinary bladder in a horse.

A 14-year-old Hanoverian gelding was evaluated after a 10-week history of occasional straining during urination and dark red urine production after exercise. Physical examination findings were within normal limits. After 2 weeks of clinical signs, ultrasonography had found no abnormalities in the kidneys or bladder. A freely voided urine sample revealed an elevated protein concentration (500 mg/dL; reference range: <100 mg/dL) and few red blood cells. Vitamin C supplementation was suggested to acidify the urine, as was provision of a salt block to encourage water intake.

Large-scale asymmetric synthesis of a cathepsin S inhibitor.

A potent reversible inhibitor of the cysteine protease cathepsin-S was prepared on large scale using a convergent synthetic route, free of chromatography and cryogenics. Late-stage peptide coupling of a chiral urea acid fragment with a functionalized aminonitrile was employed to prepare the target, using 2-hydroxypyridine as a robust, nonexplosive replacement for HOBT. The two key intermediates were prepared using a modified Strecker reaction for the aminonitrile and a phosphonation-olefination-rhodium-catalyzed asymmetric hydrogenation sequence for the urea. A palladium-catalyzed vinyl transfer coupled with a Claisen reaction was used to produce the aldehyde required for the side chain. Key scale up issues, safety calorimetry, and optimization of all steps for multikilogram production are discussed.