Protonolysis of a Ruthenium–Carbene Bond and Applications in Olefin Metathesis

The synthesis of a ruthenium complex containing an N-heterocylic carbene (NHC) and a mesoionic carbene (MIC) is described wherein addition of a Brønsted acid results in protonolysis of the Ru–MIC bond to generate an extremely active metathesis catalyst. Mechanistic studies implicated a rate-determining protonation step in the generation of the metathesis-active species. The activity of the NHC/MIC catalyst was found to exceed those of current commercial ruthenium catalysts

Synthesis of Highly Stable 1,3-Diaryl-1H-1,2,3-triazol-5-ylidenes and Their Applications in Ruthenium-Catalyzed Olefin Metathesis

The formal cycloaddition between 1,3-diaza-2-azoniaallene salts and alkynes or alkyne equivalents provides an efficient synthesis of 1,3-diaryl-1H-1,2,3-triazolium salts, the direct precursors of 1,2,3-triazol-5-ylidenes. These N,N-diarylated mesoionic carbenes (MICs) exhibit enhanced stability in comparison to their alkylated counterparts. Experimental and computational results confirm that these MICs act as strongly electron-donating ligands. Their increased stability allows for the preparation of ruthenium olefin metathesis catalysts that are efficient in both ring-opening and ring-closing reactions

Creation of multiple nanodots by single ions

In the challenging search for tools that are able to modify surfaces on the nanometer scale, heavy ions with energies of several 10 MeV are becoming more and more attractive. In contrast to slow ions where nuclear stopping is important and the energy is dissipated into a large volume in the crystal, in the high energy regime the stopping is due to electronic excitations only. Because of the extremely local (< 1 nm) energy deposition with densities of up to 10E19 W/cm^2, nanoscaled hillocks can be created under normal incidence. Usually, each nanodot is due to the impact of a single ion and the dots are randomly distributed. We demonstrate that multiple periodically spaced dots separated by a few 10 nanometers can be created by a single ion if the sample is irradiated under grazing angles of incidence. By varying this angle the number of dots can be controlled.Comment: 12 pages, 6 figure

Long-term efficacy and safety outcomes with OROS-MPH in adults with ADHD

Methylphenidate (MPH) is widely prescribed for adults with attention deficit hyperactivity disorder (ADHD), but data on long-term treatment and maintenance of effect are lacking. Osmotic release oral system-methylphenidate (OROS–MPH) was evaluated in a 52-wk open-label study in subjects who had previously completed a short-term placebo-controlled trial and short-term open-label extension. Efficacy was assessed using the investigator- and subject-rated Conners’ Adult ADHD Rating Scales (CAARS:O-SV and CAARS:S-S), and the Clinical Global Impression – Severity (CGI-S), Sheehan Disability Scale (SDS) and Quality of Life Enjoyment and Satisfaction Questionnaire (Q-LES-Q). Subjects completing ≥52 wk of treatment were eligible for a 4-wk randomized, placebo-controlled withdrawal phase in which loss of treatment effect was assessed using CAARS:O-SV and CGI-S. In the open-label phase (n=156), mean CAARS:O-SV score decreased from baseline by 1.9±7.8 (p<0.01), and small, statistically significant improvements from baseline were observed for CAARS:S-S, CGI-S and SDS. In the double-blind phase (OROS-MPH, n=23; placebo, n=22), CAARS:O-SV increased from double-blind baseline in the OROS-MPH and placebo arms (4.0±7.6 vs. 6.5±7.8, not statistically significant). Long-term OROS-MPH treatment was well tolerated, and there was no evidence of withdrawal or rebound after discontinuation. In conclusion, the short-term benefits of OROS-MPH continue during long-term open-label treatment. Maintenance of efficacy in a placebo-controlled withdrawal design remains to be confirmed in larger patient populations

Midgap edge states and pairing symmetry of quasi-one-dimensional organic superconductors

The singlet s-, d- and triplet p-wave pairing symmetries in quasi-one-dimensional organic superconductors can be experimentally discriminated by probing the Andreev bound states at the sample edges. These states have the energy in the middle of the superconducting gap and manifest themselves as a zero-bias peak in tunneling conductance into the corresponding edge. Their existence is related to the sign change of the pairing potential around the Fermi surface. We present an exact self-consistent solution of the edge problem showing the presence of the midgap states for p_x-wave superconductivity. The spins of the edge state respond paramagnetically to a magnetic field parallel to the vector d that characterizes triplet pairing.Comment: 6 pages, 4 figures. V.2: New section on spin response is added and references are updated. V.3: Final version accepted to PRB. Typos are corrected and important note is added in proof

Possible Triplet Electron Pairing and an Anisotropic Spin Susceptibility in Organic Superconductors (TMTSF)_2 X

We argue that (TMTSF)_2 PF_6 compound under pressure is likely a triplet superconductor with a vector order parameter d(k) \equiv (d_a(k) \neq 0, d_c(k) = ?, d_{b'}(k) = 0); |d_a(k)| > |d_c(k)|. It corresponds to an anisotropic spin susceptibility at T=0: \chi_{b'} = \chi_0, \chi_a \ll \chi_0, where \chi_0 is its value in a metallic phase. [The spin quantization axis, z, is parallel to a so-called b'-axis]. We show that the suggested order parameter explains why the upper critical field along the b'-axis exceeds all paramagnetic limiting fields, including that for a nonuniform superconducting state, whereas the upper critical field along the a-axis (a \perp b') is limited by the Pauli paramagnetic effects [I. J. Lee, M. J. Naughton, G. M. Danner and P. M. Chaikin, Phys. Rev. Lett. 78, 3555 (1997)]. The triplet order parameter is in agreement with the recent Knight shift measurements by I. J. Lee et al. as well as with the early results on a destruction of superconductivity by nonmagnetic impurities and on the absence of the Hebel-Slichter peak in the NMR relaxation rate.Comment: 4 pages, 1 eps figur

Pairing Symmetry Competition in Organic Superconductors

A review is given on theoretical studies concerning the pairing symmetry in organic superconductors. In particular, we focus on (TMTSF)$_2$X and $\kappa$-(BEDT-TTF)$_2$X, in which the pairing symmetry has been extensively studied both experimentally and theoretically. Possibilities of various pairing symmetry candidates and their possible microscopic origin are discussed. Also some tests for determining the actual pairing symmtery are surveyed.Comment: 16 pages, 8 figures, to be published in J. Phys. Soc. Jpn., special issue on "Organic Conductors

Pairing competition in a quasi-one-dimensional model of organic superconductors (TMTSF)2X_{2}X in magnetic field

We microscopically study the effect of the magnetic field (Zeeman splitting) on the superconducting state in a model for quasi-one-dimensional organic superconductors (TMTSF)$_{2}X$. We investigate the competition between spin singlet and spin triplet pairings and the Fulde-Ferrell-Larkin-Ovchinnikov(FFLO) state by random phase approximation. While we studied the competition by comparison with the eigenvalue of the gap equation at a fixed temperature in our previous study (Phys. Rev. Lett. \textbf{102} (2009) 016403), here we obtain both the $T_c$ for each pairing state and a phase diagram in the $T$(temperature)-$h_z$(field)-$V_y$(strength of the charge fluctuation) space. The phase diagram shows that consecutive transitions from singlet pairing to the FFLO state and further to $S_z=1$ triplet pairing can occur upon increasing the magnetic field when $2k_{F}$ charge fluctuations coexist with $2k_{F}$ spin fluctuations. In the FFLO state, the singlet d-wave and $S_{z}=0$ triplet $f$-wave components are strongly mixed especially when the charge fluctuations are strong.Comment: 11 pages, 9 figure

Measurements of fiducial and differential cross sections for Higgs boson production in the diphoton decay channel at s√=8 TeV with ATLAS

Measurements of fiducial and differential cross sections are presented for Higgs boson production in proton-proton collisions at a centre-of-mass energy of s√=8 TeV. The analysis is performed in the H → γγ decay channel using 20.3 fb−1 of data recorded by the ATLAS experiment at the CERN Large Hadron Collider. The signal is extracted using a fit to the diphoton invariant mass spectrum assuming that the width of the resonance is much smaller than the experimental resolution. The signal yields are corrected for the effects of detector inefficiency and resolution. The pp → H → γγ fiducial cross section is measured to be 43.2 ±9.4(stat.) − 2.9 + 3.2 (syst.) ±1.2(lumi)fb for a Higgs boson of mass 125.4GeV decaying to two isolated photons that have transverse momentum greater than 35% and 25% of the diphoton invariant mass and each with absolute pseudorapidity less than 2.37. Four additional fiducial cross sections and two cross-section limits are presented in phase space regions that test the theoretical modelling of different Higgs boson production mechanisms, or are sensitive to physics beyond the Standard Model. Differential cross sections are also presented, as a function of variables related to the diphoton kinematics and the jet activity produced in the Higgs boson events. The observed spectra are statistically limited but broadly in line with the theoretical expectations