The oxidation of ethylene-1,2-d2 over a silver catalyst studied by microwave spectroscopy

Stereospecific ethylene-1,2-d2 was oxidized to ethylene oxide-1,2-d2 over Ag catalysts in a flow reactor at 180-280 [deg]C. The epoxide products did not completely randomize for any of the reaction conditions explored. Using a catalyst with good selectivity, 57.5 +/- 1% of the epoxide had the same configuration as the starting material; with a less selective catalyst 54.0 +/- 1% was found. Variation of temperature did not affect the results for either catalyst. It was possible to increase slightly the percentage retention by decreasing the catalyst bed or increasing the flow rate through the reactor. Types of surface processes that can be eliminated by these observations were discussed as well as several hypotheses that can account for the deviations from complete randomization.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/22627/1/0000177.pd

Inhibition of the \u3cem\u3edapE\u3c/em\u3e-Encoded \u3cem\u3eN\u3c/em\u3e-Succinyl- ʟ, ʟ-diaminopimelic Acid Desuccinylase from \u3cem\u3eNeisseria meningitidis\u3c/em\u3e by ʟ-Captopril

Binding of the competitive inhibitor ʟ-captopril to the dapE-encoded N-succinyl-ʟ, ʟ-diaminopimelic acid desuccinylase from Neisseria meningitidis (NmDapE) was examined by kinetic, spectroscopic, and crystallographic methods. ʟ-Captopril, an angiotensin-converting enzyme (ACE) inhibitor, was previously shown to be a potent inhibitor of the DapE from Haemophilus influenzae (HiDapE) with an IC50 of 3.3 μM and a measured Ki of 1.8 μM and displayed a dose-responsive antibiotic activity toward Escherichia coli. ʟ-Captopril is also a competitive inhibitor of NmDapE with a Ki of 2.8 μM. To examine the nature of the interaction of ʟ-captopril with the dinuclear active site of DapE, we have obtained electron paramagnetic resonance (EPR) and magnetic circular dichroism (MCD) data for the enzymatically hyperactive Co(II)-substituted forms of both HiDapE and NmDapE. EPR and MCD data indicate that the two Co(II) ions in DapE are antiferromagnetically coupled, yielding an S = 0 ground state, and suggest a thiolate bridge between the two metal ions. Verification of a thiolate-bridged dinuclear complex was obtained by determining the three-dimensional X-ray crystal structure of NmDapE in complex with ʟ-captopril at 1.8 Å resolution. Combination of these data provides new insights into binding of ʟ-captopril to the active site of DapE enzymes as well as important inhibitor–active site residue interaction’s. Such information is critical for the design of new, potent inhibitors of DapE enzymes

Cloud and Thermodynamic Parameters Retrieved from Satellite Ultraspectral Infrared Measurements

Atmospheric-thermodynamic parameters and surface properties are basic meteorological parameters for weather forecasting. A physical geophysical parameter retrieval scheme dealing with cloudy and cloud-free radiance observed with satellite ultraspectral infrared sounders has been developed and applied to the Infrared Atmospheric Sounding Interferometer (IASI) and the Atmospheric InfraRed Sounder (AIRS). The retrieved parameters presented herein are from radiance data gathered during the Joint Airborne IASI Validation Experiment (JAIVEx). JAIVEx provided intensive aircraft observations obtained from airborne Fourier Transform Spectrometer (FTS) systems, in-situ measurements, and dedicated dropsonde and radiosonde measurements for the validation of the IASI products. Here, IASI atmospheric profile retrievals are compared with those obtained from dedicated dropsondes, radiosondes, and the airborne FTS system. The IASI examples presented here demonstrate the ability to retrieve fine-scale horizontal features with high vertical resolution from satellite ultraspectral sounder radiance spectra

Dynamics of Wetting Fronts in Porous Media

We propose a new phenomenological approach for describing the dynamics of wetting front propagation in porous media. Unlike traditional models, the proposed approach is based on dynamic nature of the relation between capillary pressure and medium saturation. We choose a modified phase-field model of solidification as a particular case of such dynamic relation. We show that in the traveling wave regime the results obtained from our approach reproduce those derived from the standard model of flow in porous media. In more general case, the proposed approach reveals the dependence of front dynamics upon the flow regime.Comment: 4 pages, 2 figures, revte

Physical Electronics

Contains research objectives and reports on four research projects

Gender and sexual orientation differences in cognition across adulthood : age is kinder to women than to men regardless of sexual orientation

Despite some evidence of greater age-related deterioration of the brain in males than in females, gender differences in rates of cognitive aging have proved inconsistent. The present study employed web-based methodology to collect data from people aged 20-65 years (109,612 men; 88,509 women). As expected, men outperformed women on tests of mental rotation and line angle judgment, whereas women outperformed men on tests of category fluency and object location memory. Performance on all tests declined with age but significantly more so for men than for women. Heterosexuals of each gender generally outperformed bisexuals and homosexuals on tests where that gender was superior; however, there were no clear interactions between age and sexual orientation for either gender. At least for these particular tests from young adulthood to retirement, age is kinder to women than to men, but treats heterosexuals, bisexuals, and homosexuals just the same

Bipolar disorder with binge eating behavior: a genome-wide association study implicates PRR5-ARHGAP8

Bipolar disorder (BD) is associated with binge eating behavior (BE), and both conditions are heritable. Previously, using data from the Genetic Association Information Network (GAIN) study of BD, we performed genome-wide association (GWA) analyses of BD with BE comorbidity. Here, utilizing data from the Mayo Clinic BD Biobank (969 BD cases, 777 controls), we performed a GWA analysis of a BD subtype defined by BE, and case-only analysis comparing BD subjects with and without BE. We then performed a meta-analysis of the Mayo and GAIN results. The meta-analysis provided genome-wide significant evidence of association between single nucleotide polymorphisms (SNPs) in PRR5-ARHGAP8 and BE in BD cases (rs726170 OR=1.91, P=3.05E-08). In the meta-analysis comparing cases with BD with comorbid BE vs. non-BD controls, a genome-wide significant association was observed at SNP rs111940429 in an intergenic region near PPP1R2P5 (p=1.21E-08). PRR5-ARHGAP8 is a read-through transcript resulting in a fusion protein of PRR5 and ARHGAP8. PRR5 encodes a subunit of mTORC2, a serine/threonine kinase that participates in food intake regulation, while ARHGAP8 encodes a member of the RhoGAP family of proteins that mediate cross-talk between Rho GTPases and other signaling pathways. Without BE information in controls, it is not possible to determine whether the observed association reflects a risk factor for BE in general, risk for BE in individuals with BD, or risk of a subtype of BD with BE. The effect of PRR5-ARHGAP8 on BE risk thus warrants further investigation

Retrieval with Infrared Atmospheric Sounding Interferometer and Validation during JAIVEx

A state-of-the-art IR-only retrieval algorithm has been developed with an all-season-global EOF Physical Regression and followed by 1-D Var. Physical Iterative Retrieval for IASI, AIRS, and NAST-I. The benefits of this retrieval are to produce atmospheric structure with a single FOV horizontal resolution (approx. 15 km for IASI and AIRS), accurate profiles above the cloud (at least) or down to the surface, surface parameters, and/or cloud microphysical parameters. Initial case study and validation indicates that surface, cloud, and atmospheric structure (include TBL) are well captured by IASI and AIRS measurements. Coincident dropsondes during the IASI and AIRS overpasses are used to validate atmospheric conditions, and accurate retrievals are obtained with an expected vertical resolution. JAIVEx has provided the data needed to validate the retrieval algorithm and its products which allows us to assess the instrument ability and/or performance. Retrievals with global coverage are under investigation for detailed retrieval assessment. It is greatly desired that these products be used for testing the impact on Atmospheric Data Assimilation and/or Numerical Weather Prediction

The theory of pulsar winds and nebulae

We review current theoretical ideas on pulsar winds and their surrounding nebulae. Relativistic MHD models of the wind of the aligned rotator, and of the striped wind, together with models of magnetic dissipation are discussed. It is shown that the observational signature of this dissipation is likely to be point-like, rather than extended, and that pulsed emission may be produced. The possible pulse shapes and polarisation properties are described. Particle acceleration at the termination shock of the wind is discussed, and it is argued that two distinct mechanisms must be operating, with the first-order Fermi mechanism producing the high-energy electrons (above 1 TeV) and either magnetic annihilation or resonant absorption of ion cyclotron waves responsible for the 100 MeV to 1 TeV electrons. Finally, MHD models of the morphology of the nebula are discussed and compared with observation.Comment: 33 pages, to appear in Springer Lecture Notes on "Neutron stars and pulsars, 40 years after the discovery", ed W.Becke