Characterization and Dynamics of Substituted Ruthenacyclobutanes Relevant to the Olefin Cross-Metathesis Reaction

The reaction of the phosphonium alkylidene [(H_(2)IMes)RuCl2═CHP(Cy)_3)]^(+) BF_(4)^− with propene, 1-butene, and 1-hexene at −45 °C affords various substituted, metathesis-active ruthenacycles. These metallacycles were found to equilibrate over extended reaction times in response to decreases in ethylene concentrations, which favored increased populations of α-monosubstituted and α,α′-disubstituted (both cis and trans) ruthenacycles. On an NMR time scale, rapid chemical exchange was found to preferentially occur between the β-hydrogens of the cis and trans stereoisomers prior to olefin exchange. Exchange on an NMR time scale was also observed between the α- and β-methylene groups of the monosubstituted ruthenacycle (H_(2)IMes)Cl_(2)Ru(CHRCH_(2)CH_(2)) (R = CH_3, CH_(2)CH_3, (CH_2)_)_(3)CH_3). EXSY NMR experiments at −87 °C were used to determine the activation energies for both of these exchange processes. In addition, new methods have been developed for the direct preparation of metathesis-active ruthenacyclobutanes via the protonolysis of dichloro(1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)(benzylidene) bis(pyridine)ruthenium(II) and its 3-bromopyridine analogue. Using either trifluoroacetic acid or silica-bound toluenesulfonic acid as the proton source, the ethylene-derived ruthenacyclobutane (H_(2)IMes)Cl_(2)Ru(CH_(2)CH_(2)CH_(2)) was observed in up to 98% yield via NMR at −40 °C. On the basis of these studies, mechanisms accounting for the positional and stereochemical exchange within ruthenacyclobutanes are proposed, as well as the implications of these dynamics toward olefin metathesis catalyst and reaction design are described

Ruthenium Metallacycles Derived from 14-Electron Complexes. New Insights into Olefin Metathesis Intermediates

Ruthenium(IV) metallacycles derived from both ethylene and propene are reported. The propene-derived metallacycles represent the first observed examples of substituted ruthenacyclobutanes and offer new insight into the preferred stereochemical orientation about metathesis intermediates. In addition, a metallacycle possessing an unsymmetrical N-heterocyclic carbene (NHC) ligand was prepared and investigated to ascertain the dynamics of the NHC relative to the metallacycle ring. Metallacycles investigated were found to possess exchange cross-peaks between the α- and β-positions in the 2D NMR, indicating a dynamic structure. The implications of these results to the mechanism of ruthenium-catalyzed olefin metathesis are discussed

Retention of mouth-to-mouth, mouth-to-mask and mouth-to-face shield ventilation

Background: Retention of mouth-to-mouth, mouth-to-mask and mouth-to-face shield ventilation techniques is poorly understood.Methods: A prospective randomised clinical trial was undertaken in January 2004 in 70 candidates randomly assigned to training in mouth-to-mouth, mouth-to-mask or mouth-to-face shield ventilation. Each candidate was trained for 10 min, after which tidal volume, respiratory rate, minute volume, peak airway pressure and the presence or absence of stomach inflation were measured. 58 subjects were reassessed 1 year later and study parameters were recorded again. Data were analysed with ANOVA, \textgreekq2 and McNemar tests.Results: Tidal volume, minute volume, peak airway pressure, ventilation rate and stomach inflation rate increased significantly at reassessment with all ventilation techniques compared with the initial assessment. However, at reassessment, mean (SD) tidal volume (960 (446) vs 1008 (366) vs 1402 (302) ml; p<0.05), minute volume (12 (5) vs 13 (7) vs 18 (3) l/min; p<0.05), peak airway pressure (14 (8) vs 17 (13) vs 25 (8) cm H2O; p<0.05) and stomach inflation rate (63% vs 58% vs 100%; p<0.05) were significantly lower with mouth-to-mask and mouth-to-face shield ventilation than with mouth-to-mouth ventilation. The ventilation rate at reassessment did not differ significantly between the ventilation techniques.Conclusions: One year after a single episode of ventilation training, lay persons tended to hyperventilate; however, the degree of hyperventilation and resulting stomach inflation were lower when a mouth-to-mask or a face shield device was employed. Regular training is therefore required to retain ventilation skills; retention of skills may be better with ventilation devices

Raman solitons in transient SRS

We report the observation of Raman solitons on numerical simulations of transient stimulated Raman scattering (TSRS) with small group velocity dispersion. The theory proceeds with the inverse scattering transform (IST) for initial-boundary value problems and it is shown that the explicit theoretical solution obtained by IST for a semi-infinite medium fits strikingly well the numerical solution for a finite medium. We understand this from the rapid decrease of the medium dynamical variable (the potential of the scattering theory). The spectral transform reflection coefficient can be computed directly from the values of the input and output fields and this allows to see the generation of the Raman solitons from the numerical solution. We confirm the presence of these nonlinear modes in the medium dynamical variable by the use of a discrete spectral analysis.Comment: LaTex file, to appear in Inverse Problem

Advanced methodology for storm sewer design—phase II

This report describes further development of computer models for determining the diameter, slope and elevations of each pipe in a storm drainage system in which the layout and manhole locations are specified. The design procedure is based on a least-cost criterion and utilizes discrete differential dynamic programming as the search technique. In this phase of the study a detention storage capability has been added to the model using two approaches. The first approach requires the specification of a maximum allowable outflow and computes the required storage. The second approach determines the storage volume such that the sum of the storage and pipe system costs is a minimum. The procedure for computation of expected damage costs has been changed to reflect the variation of flood damage with flood volume. Also a surface runoff component has been added. This option uses the hydrograph generation portion of the Illinois Urbana Drainage Area Simulator model. Improved cost specification methods as well as flexible pipe elevation constraint capabilities have been added. The new developments are illustrated using two example basins.U.S. Department of the InteriorU.S. Geological SurveyOpe

Designable electron transport features in one-dimensional arrays of metallic nanoparticles: Monte Carlo study of the relation between shape and transport

We study the current and shot noise in a linear array of metallic nanoparticles taking explicitly into consideration their discrete electronic spectra. Phonon assisted tunneling and dissipative effects on single nanoparticles are incorporated as well. The capacitance matrix which determines the classical Coulomb interaction within the capacitance model is calculated numerically from a realistic geometry. A Monte Carlo algorithm which self-adapts to the size of the system allows us to simulate the single-electron transport properties within a semiclassical framework. We present several effects that are related to the geometry and the one-electron level spacing like e.g. a negative differential conductance (NDC) effect. Consequently these effects are designable by the choice of the size and arrangement of the nanoparticles.Comment: 13 pages, 12 figure

Methods for removal of unwanted signals from gravity time-series : comparison using linear techniques complemented with analysis of system dynamics

We thanks the participants of the 35th General Assembly of the European Seismological Commission for comments on preliminary results. The authors are grateful to all IGETS contributors, particularly to the station operators and to ISDC/GFZ-Potsdam for providing the original gravity data used in this study. We also thank the developers of ATLANTIDA3.1 and UTide. Part of this work was performed using the ICSMB High Performance Computing Cluster, University of Aberdeen. We also thanks M. Thiel and A. Moura for reviewing a preliminary version and making comments on the methods section and M.A. Ara´ujo for comments on Lyapunov exponents. Funding: A. Valencio is supported by CNPq, Brazil [206246/2014-5]; and received a travel grant from the School of Natural and Computing Sciences, University of Aberdeen [PO2073498], for a presentation including preliminary results.Peer reviewedPostprintPublisher PD

A new two-pole accretion polar: RX J1846.9+5538

We report the discovery of a new, bright (V = 17 mag) AM Her system as the optical counterpart of the soft ROSAT All-Sky-Survey source RX J1846.9+5538 (= 1RXS J184659.4+553834). Optical photometric and spectroscopic follow-up observations reveal a single period of 128.7 min, consistent with a high degree of spin-orbit synchronization, and a low polar field strength ($B<20$ MG) of the primary accretion region. The system was observed in optical intermediate and high states that differ by about 1 mag. These brightness variations were accompanied by a correlated change of the optical light curve, which we interpret as a switch between one- and two-pole accretion. This explanation is also supported by the X-ray light curves, which at two different epochs display emission from two equally bright accretion regions separated by 160 degrees. Both spots possess distinct spectral X-ray properties as seen from the X-ray hardness ratio, where the secondary accretion region appears significantly softer, thus probably indicating a higher field strength compared to the primary region. In all ROSAT pointings a deep dip is present during the primary flux maxima, very likely caused by absorption in one of the accretion streams.Comment: 11 pages, 9 figures; accepted for publication in Astronomy & Astrophysic