Stereoelectronic effects on the binding of neutral Lewis bases to CdSe nanocrystals

Using P-31 nuclear magnetic resonance (NMR) spectroscopy, we monitor the competition between tri-nbutylphosphine (Bu3P) and various amine and phosphine ligands for the surface of chloride terminated CdSe nanocrystals. Distinct P-31 NMR signals for free and bound phosphine ligands allow the surface ligand coverage to be measured in phosphine solution. Ligands with a small steric profile achieve higher surface coverages (Bu3P = 0.5 nm(-2), Me2P-n-octyl = 2.0 nm(-2), NH2Bu = >3 nm(-2)) and have greater relative binding affinity for the nanocrystal (binding affinity: Me3P > Me2P -n-octyl similar to Me2P -n-octadecyl > Et3P > Bu3P). Among phosphines, only Bu 3 P and Me2P-n-octyl support a colloidal dispersion, allowing a relative surface binding affinity (K-rel) to be estimated in that case (K-rel = 3.1). The affinity of the amine ligands is measured by the extent to which they displace Bu3P from the nanocrystals (K-rel: H2NBu similar to N-n-butylimidazole > 4-ethylpyridine > Bu3P similar to HNBu2 > Me2NBu > Bu3N). The affinity for the CdSe surface is greatest among soft, basic donors and depends on the number of each ligand that bind. Sterically unencumbered ligands such as imidazole, pyridine, and n-alkylamines can therefore outcompete stronger donors such as alkylphosphines. The influence of repulsive interactions between ligands on the binding affinity is a consequence of the high atom density of binary semiconductor surfaces. The observed behavior is distinct from the self-assembly of straight-chain surfactants on gold and silver where the ligands are commensurate with the underlying lattice and attractive interactions between aliphatic chains strengthen the binding

Studying Driver Behavior in Self Driving Cars Using a Driving Simulator

Undergraduate Research Opportunity Program (UROP)http://deepblue.lib.umich.edu/bitstream/2027.42/116120/1/Studying_Driver_Behavior_SelfDrivingCars.pd

Constraints on the origin of the ultra-high energy cosmic-rays using cosmic diffuse neutrino flux limits: An analytical approach

Astrophysical neutrinos are expected to be produced in the interactions of ultra-high energy cosmic-rays with surrounding photons. The fluxes of the astrophysical neutrinos are highly dependent on the characteristics of the cosmic-ray sources, such as their cosmological distributions. We study possible constraints on the properties of cosmic-ray sources in a model-independent way using experimentally obtained diffuse neutrino flux above 100 PeV. The semi-analytic formula is derived to estimate the cosmogenic neutrino fluxes as functions of source evolution parameter and source extension in redshift. The obtained formula converts the upper-limits on the neutrino fluxes into the constraints on the cosmic-ray sources. It is found that the recently obtained upper-limit on the cosmogenic neutrinos by IceCube constrains the scenarios with strongly evolving ultra-high energy cosmic-ray sources, and the future limits from an 1 km^3 scale detector are able to further constrain the ultra-high energy cosmic-rays sources with evolutions comparable to the cosmic star formation rate.Comment: 9 pages, 3 figures and 1 table. Accepted by Phys. Rev.

Electrophysiological responses to argument structure violations in healthy adults and individuals with nonfluent aphasia

Agrammatic individuals show impaired production of verbs with complex argument structure. Whether these participants show argument structure deficits during comprehension, however, is unclear. The present study investigated this issue by examining electrophysiological responses to argument structure violations in agrammatic individuals and healthy adults. Results showed that unlike control participants, who evinced a negative effect followed by a positive shift (N400-P600) in response to argument structure violations, individuals with agrammatic aphasia showed a P600 response only. This suggests impaired real time processing of the thematic requirements of verbs

Multiwavelength studies of G298.6−-0.0: An old GeV supernova remnant interacting with molecular clouds

Hadronic $\gamma$-ray sources associated with supernova remnants (SNRs) can serve as stopwatches for the escape of cosmic rays from SNRs, which gradually develops from highest-energy particles to lowest-energy particles with time. In this work, we analyze the 13.7~yr \emph{Fermi}-LAT data to investigate the $\gamma$-ray feature in/around the SNR G298.6$-$0.0 region. With $\gamma$-ray spatial analyses, we detect three point-like components. Among them, Src-NE is at the eastern SNR shell, and Src-NW is adjacent to the western edge of this SNR. Src-NE and Src-NW demonstrate spectral breaks at energies around/below 1.8~GeV, suggesting an old SNR age of $>$10~kyr. We also look into the X-ray emission from the G298.6$-$0.0 region, with the Chandra-ACIS data. We detected an extended keV source having a centrally filled structure inside the radio shell. The X-ray spectra are well fit by a model which assumes a collisional ionisation equilibrium of the thermal plasma, further supporting an old SNR age. Based on our analyses of the NANTEN CO- and ATCA-Parkes HI-line data, we determined a kinematic distance of $\sim$10.1~kpc from us to G298.6$-$0.0. This distance entails a large physical radius of the SNR of $\sim$15.5~pc, which is an additional evidence for an old age of $>$10~kyr. Besides, the CO data cube enables us to three-dimensionally locate the molecular clouds (MCs) which are potentially interacting with SNR G298.6$-$0.0 and could account for the hadronic $\gamma$-rays detected at Src-NE or Src-NW. Furthermore, the multiwavelength observational properties unanimously imply that the SNR--MC interaction occurs mainly in the northeast direction.Comment: Accepted by Publications of the Astronomical Society of Japan (PASJ) on 16-Jan-202

Descending aortic calcification increases renal dysfunction and in-hospital mortality in cardiac surgery patients with intraaortic balloon pump counterpulsation placed perioperatively : a case control study

Introduction: Acute kidney injury (AKI) after cardiac surgery increases length of hospital stay and in-hospital mortality. A significant number of patients undergoing cardiac surgical procedures require perioperative intra-aortic balloon pump (IABP) support. Use of an IABP has been linked to an increased incidence of perioperative renal dysfunction and death. This might be due to dislodgement of atherosclerotic material in the descending thoracic aorta (DTA). Therefore, we retrospectively studied the correlation between DTA atheroma, AKI and in-hospital mortality. Methods: A total of 454 patients were retrospectively matched to one of four groups: -IABP/-DTA atheroma, +IABP/-DTA atheroma, -IABP/+DTA atheroma, +IABP/+DTA atheroma. Patients were then matched according to presence/absence of DTA atheroma, presence/absence of IABP, performed surgical procedure, age, gender and left ventricular ejection fraction (LVEF). DTA atheroma was assessed through standard transesophageal echocardiography (TEE) imaging studies of the descending thoracic aorta. Results: Basic patient characteristics, except for age and gender, did not differ between groups. Perioperative AKI in patients with -DTA atheroma/+IABP was 5.1% versus 1.7% in patients with -DTA atheroma/-IABP. In patients with +DTA atheroma/+IABP the incidence of AKI was 12.6% versus 5.1% in patients with +DTA atheroma/-IABP. In-hospital mortality in patients with +DTA atheroma/-IABP was 3.4% versus 8.4% with +DTA atheroma/+IABP. In patients with +DTA atheroma/+IABP in hospital mortality was 20.2% versus 6.4% with +DTA atheroma/-IABP. Multivariate logistic regression identified DTA atheroma > 1 mm (P = *0.002, odds ratio (OR) = 4.13, confidence interval (CI) = 1.66 to 10.30), as well as IABP support (P = *0.015, OR = 3.04, CI = 1.24 to 7.45) as independent predictors of perioperative AKI and increased in-hospital mortality. DTA atheroma in conjunction with IABP significantly increased the risk of developing acute kidney injury (P = 0.0016) and in-hospital mortality (P = 0.0001) when compared to control subjects without IABP and without DTA atheroma. Conclusions: Perioperative IABP and DTA atheroma are independent predictors of perioperative AKI and in-hospital mortality. Whether adding an IABP in patients with severe DTA calcification increases their risk of developing AKI and mortality postoperatively cannot be clearly answered in this study. Nevertheless, when IABP and DTA are combined, patients are more likely to develop AKI and to die postoperatively in comparison to patients without IABP and DTA atheroma

Fine Structures of Shock of SN 1006 with the Chandra Observation

The north east shell of SN 1006 is the most probable acceleration site of high energy electrons (up to ~ 100 TeV) with the Fermi acceleration mechanism at the shock front. We resolved non-thermal filaments from thermal emission in the shell with the excellent spatial resolution of Chandra. The thermal component is extended widely over about ~ 100 arcsec (about 1 pc at 1.8 kpc distance) in width, consistent with the shock width derived from the Sedov solution. The spectrum is fitted with a thin thermal plasma of kT = 0.24 keV in non-equilibrium ionization (NEI), typical for a young SNR. The non-thermal filaments are likely thin sheets with the scale widths of ~ 4 arcsec (0.04 pc) and ~ 20 arcsec (0.2 pc) at upstream and downstream, respectively. The spectra of the filaments are fitted with a power-law function of index 2.1--2.3, with no significant variation from position to position. In a standard diffusive shock acceleration (DSA) model, the extremely small scale length in upstream requires the magnetic field nearly perpendicular to the shock normal. The injection efficiency (eta) from thermal to non-thermal electrons around the shock front is estimated to be ~ 1e-3 under the assumption that the magnetic field in upstream is 10 micro G. In the filaments, the energy densities of the magnetic field and non-thermal electrons are similar to each other, and both are slightly smaller than that of thermal electrons. in the same order for each other. These results suggest that the acceleration occur in more compact region with larger efficiency than previous studies.Comment: 24 pages, 11 figures, Accepted for publication in ApJ, the paper with full resolution images in http://www-cr.scphys.kyoto-u.ac.jp/member/bamba/Paper/SN1006.pd

Bimetallic Coordination Insertion Polymerization of Unprotected Polar Monomers: Copolymerization of Amino Olefins and Ethylene by Dinickel Bisphenoxyiminato Catalysts

Dinickel bisphenoxyiminato complexes based on highly substituted p- and m-terphenyl backbones were synthesized, and the corresponding atropisomers were isolated. In the presence of a phosphine scavenger, Ni(COD)_2, the phosphine-ligated syn-dinickel complexes copolymerized α-olefins and ethylene in the presence of amines to afford 0.2–1.3% α-olefin incorporation and copolymerized amino olefins and ethylene with a similar range of incorporation (0.1–0.8%). The present rigid catalysts provide a bimetallic strategy for insertion polymerization of polar monomers without masking of the heteroatom group. The effects of the catalyst structure on the reactivity were studied by comparisons of the syn and anti atropisomers and the p- and m-terphenyl systems

Diffuse Hard X-ray Sources Discovered with the ASCA Galactic Plane Survey

We found diffuse hard X-ray sources, G11.0+0.0, G25.5+0.0, and G26.6-0.1 in the ASCA Galactic plane survey data. The X-ray spectra are featureless with no emission line, and are fitted with both models of a thin thermal plasma in non-equilibrium ionization and a power-law function. The source distances are estimated to be 1-8 kpc, using the best-fit NH values on the assumption that the mean density in the line of sight is 1 H cm^-3. The source sizes and luminosities are then 4.5-27 pc and (0.8-23)x10^33 ergs/s. Although the source sizes are typical to supernova remnants (SNR) with young to intermediate ages, the X-ray luminosity, plasma temperature, and weak emission lines in the spectra are all unusual. This suggests that these objects are either shell-like SNRs dominated by X-ray synchrotron emission, like SN 1006, or, alternatively, plerionic SNRs. The total number of these classes of SNRs in our Galaxy is also estimated.Comment: 17 pages, 9 figures; to appear in Ap