Computed potential energy surfaces for chemical reactions

The work on the NH + NO system which was described in the last progress report was written up and a draft of the manuscript is included in the appendix. The appendix also contains a draft of a manuscript on an Ar + H + H surface. New work which was completed in the last six months includes the following: (1) calculations on the (1)CH2 + H2O, H2 + HCOH, and H2 + H2CO product channels in the CH3 + OH reaction; (2) calculations for the NH2 + O reaction; (3) calculations for the CH3 + O2 reaction; and (4) calculations for CH3O and the two decomposition channels--CH2OH and H + H2CO. Detailed descriptions of this work will be given in manuscripts; however, brief descriptions of the CH3 + OH and CH3 + O2 projects are given

Computed Potential Energy Surfaces for Chemical Reactions

A manuscript describing the calculations on the (1)CH2 + H2O, H2 + HCOH, and H2 + H2CO product channels in the CH3 + OH reaction, which were described in the last progress report, has been accepted for publication in J. Chem. Phys., and a copy of the manuscript is included in the appendix. The production of (1)CH2 in this reaction is important in hydrocarbon combustion since (1)CH2 is highly reactive and would be expected to insert into N2, possibly leading to a new source for prompt NO(x) (vide infra). During the last six months new calculations have been carried out for the NH2 + NO system, which is important in the thermal de-NO(x) process

Methanation of CO over Ni catalyst: A theoretical study

Theoretical methods (generalized valence‐bond calculations) were used to examine the bond energies and geometries of numerous species chemisorbed onto Ni clusters representing Ni surface. These results were used to obtain thermochemical information and to examine various mechanisms for the methanation of CO over Ni: CO+3H^(→)_(2(Ni)) CH_4+H_2O. It is found that chemisorbed formyl radicals (Ni–CHO) lead to a favorably appearing chain reaction that is consistent with current experimental results. In addition, we find a chemisorbed C_2 species that may be the catalytically active C_(ad) formed from dissociation of CO

Conversion of total shoulder arthroplasty to reverse shoulder arthroplasty made possible by custom humeral adapter

AbstractReverse shoulder arthroplasty (RSA) is increasingly being used to revise anatomical total shoulder arthroplasty cases. This procedure's high complication rate has been reduced by the availability of modular shoulder systems, which allows the humeral component to be preserved during the conversion. This case report describes the revision of an anatomical shoulder implant inserted in 1998. Polyethylene wear and the resulting metal-on-metal contact had caused metallosis. Since the existing humeral implant was not compatible with standard conversion products, the manufacturer provided a custom humeral adapter that allowed the humeral stem to be preserved. This approach greatly simplified the surgical procedure and resulted in good anatomical and clinical outcomes after 9 months of follow-up

Expression of a catalytically inactive mutant form of glutathione peroxidase 4 (Gpx4) confers a dominant-negative effect in male fertility.

The selenoenzyme Gpx4 is essential for early embryogenesis and cell viability for its unique function to prevent phospholipid oxidation. Recently, the cytosolic form of Gpx4 was identified as an upstream regulator of a novel form of non-apoptotic cell death, called ferroptosis, whereas the mitochondrial isoform of Gpx4 (mGpx4) was previously shown to be crucial for male fertility. Here, we generated and analyzed mice with targeted mutation of the active site selenocysteine (Sec) of Gpx4 (Gpx4_U46S). Mice homozygous for Gpx4_U46S died at the same embryonic stage (E7.5) as Gpx4-/- embryos as expected. Surprisingly, male mice heterozygous for Gpx4_U46S presented subfertility. Subfertility was manifested in a reduced number of litters from heterozygous breedings and an impairment of spermatozoa to fertilize oocytes in vitro. Morphologically, sperm isolated from heterozygous Gpx4_U46S mice revealed many structural abnormalities particularly in the spermatozoan midpiece due to improper oxidation and polymerization of sperm capsular proteins and malformation of the mitochondrial capsule surrounding and stabilizing sperm mitochondria. These findings are reminiscent of sperm isolated from selenium-deprived rodents or from mice specifically lacking mGpx4. Due to a strongly facilitated incorporation of Ser in the polypeptide chain as compared to Sec at the UGA codon, expression of the catalytically inactive Gpx4_U46S was found to be strongly increased. Since the stability of the mitochondrial capsule of mature spermatozoa depends on the moonlighting function of Gpx4 both as an enzyme oxidizing capsular protein thiols and being a structural protein, tightly controlled expression of functional Gpx4 emerges being key for full male fertility

Spatio-Temporal Variability of Suspended Particulate Matter in a High-Arctic Estuary (Adventfjorden, Svalbard) Using Sentinel-2 Time-Series

Arctic coasts, which feature land-ocean transport of freshwater, sediments, and other terrestrial material, are impacted by climate change, including increased temperatures, melting glaciers, changes in precipitation and runoff. These trends are assumed to affect productivity in fjordic estuaries. However, the spatial extent and temporal variation of the freshwater-driven darkening of fjords remain unresolved. The present study illustrates the spatio-temporal variability of suspended particulate matter (SPM) in the Adventfjorden estuary, Svalbard, using in-situ field campaigns and ocean colour remote sensing (OCRS) via high-resolution Sentinel-2 imagery. To compute SPM concentration (CSPMsat), a semi-analytical algorithm was regionally calibrated using local in-situ data, which improved the accuracy of satellite-derived SPM concentration by ~20% (MRD). Analysis of SPM concentration for two consecutive years (2019, 2020) revealed strong seasonality of SPM in Adventfjorden. Highest estimated SPM concentrations and river plume extent (% of fjord with CSPMsat > 30 mg L−1) occurred during June, July, and August. Concurrently, we observed a strong relationship between river plume extent and average air temperature over the 24 h prior to the observation (R2 = 0.69). Considering predicted changes to environmental conditions in the Arctic region, this study highlights the importance of the rapidly changing environmental parameters and the significance of remote sensing in analysing fluxes in light attenuating particles, especially in the coastal Arctic Ocean.publishedVersio

Temporal Trends in the Standing Broad Jump Performance of United States Children and Adolescents

Purpose: To estimate temporal trends in broad jump performance for United States youth, a marker of muscular fitness and health. Method: Electronic databases, topical systematic reviews, and personal libraries were systematically searched for studies reporting descriptive standing broad jump data for apparently healthy United States youth (age 10–17 years). Temporal trends at the sex-age level were estimated using sample-weighted regression models associating the year of testing to mean jump performance, with national trends standardized to the year 1985 using a post-stratified population-weighting procedure. Results: Collectively, there was a small increase of 12.6 cm (95%CI: 12.5 to 12.7) or 7.9% (95%CI: 7.1 to 8.6) in 65,527 United States youth between 1911 and 1990. Increases were greater for girls (change in means [95% CI]: 17.1 cm [16.9 to 17.3]; 11.4% [10.7 to 12.2]) compared to boys (change in means [95% CI]: 8.5 cm [8.3 to 8.7]; 4.6% [3.8 to 5.4]), but did not differ between children (10–12 years) and adolescents (13–17 years). Increases in broad jump performance were not always uniform across time, with steady and progressive increases observed for boys and children, respectively, and a diminishing rate of increase observed for girls and adolescents. Conclusions: Muscular fitness is a good marker of health, so greater broad jump performance from 1911 to 1990 may reflect corresponding changes in health. Routine assessment of broad jump performance may be useful to monitor trends in health and muscular fitness of United States youth due to its practicality, scalability, and predictive utility

Optical response of small silver clusters

The time-dependent local density approximation is applied to the optical response of the silver clusters, Ag_2, Ag_3, Ag_8 and Ag_9^+. The calculation includes all the electrons beyond the closed-shell Ag^{+11} ionic core, thus including for the first time explicitly the filled d-shell in the response. The excitation energy of the strong surface plasmon near 4 eV agrees well with experiment. The theoretical transition strength is quenched by a factor of 4 with respect to the pure s-electron sum rule in Ag_8 due to the d-electrons. A comparable amount of strength lies in complex states below 6 eV excitation. The total below 6 eV, about 50% of the s sum rule, is consistent with published experiments.Comment: 13 pages RevTex and 9 Postscript figure