Halide Control of N,N-Coordination versus N,C-Cyclometalation and Stereospecific Phenyl Ring Deuteration of Osmium(II) p-Cymene Phenylazobenzothiazole Complexes

YesWe report the synthesis of halido Os(II) p-cymene complexes bearing bidentate chelating phenylazobenzothiazole (AZBTZ) ligands. Unlike the analogous phenylazopyridine (AZPY) complexes, AZBTZ-NMe2 is capable of both N,N-coordination to Os(II) and cyclometalation to form N,C-coordinated species. N,C-Coordination occurs via an azo nitrogen and an ortho carbon on the aniline ring, as identified by 1H NMR and X-ray crystallography of [Os(p-cym)(N,N-AZBTZ-NMe2)Cl]PF6 (1a), [Os(p-cym)(N,N-AZBTZ-NMe2)Br]PF6 (2a), [Os(p-cym)(N,C-AZBTZ-NMe2)Br] (2b), and [Os(p-cym)(N,C-AZBTZ-NMe2)I] (3b). The N,C-coordinated species is more stable and is not readily converted to the N,N-coordinated complex. Analysis of the crystal structures suggests that their formation is influenced by steric interactions between the p-cym and AZBTZ-NMe2 ligands: in particular, larger monodentate halide ligands favor N,C-coordination. The complexes [Os(p-cym)(N,N-Me2-AZBTZ-NH2)Cl]PF6 (4) and [Os(p-cym)(N,N-Me2-AZBTZ-NH2)I]PF6 (5) were synthesized with methyl groups blocking the ortho positions on the aniline ring, forcing an N,N-coordination geometry. 1H NMR NOE experiments confirmed hindered rotation of the arene ligand and steric crowding around the metal center. Complex 2b exhibited unexpected behavior under acidic conditions, involving regiospecific deuteration of the aniline ring at the meta position, as observed by 1H NMR and high-resolution ESI-MS. Deuterium exchange occurs only under acidic conditions, suggesting an associative mechanism. The calculated partial charges on 2b show that the meta carbon is significantly more negatively charged, which may account for the regiospecificity of deuterium exchange.ERC, EPSRC, The Royal Societ

Significant out-of-sample classification from methylation profile scoring for amyotrophic lateral sclerosis

We conducted DNA methylation association analyses using Illumina 450K data from whole blood for an Australian amyotrophic lateral sclerosis (ALS) case–control cohort (782 cases and 613 controls). Analyses used mixed linear models as implemented in the OSCA software. We found a significantly higher proportion of neutrophils in cases compared to controls which replicated in an independent cohort from the Netherlands (1159 cases and 637 controls). The OSCA MOMENT linear mixed model has been shown in simulations to best account for confounders. When combined in a methylation profile score, the 25 most-associated probes identified by MOMENT significantly classified case–control status in the Netherlands sample (area under the curve, AUC = 0.65, CI95% = [0.62–0.68], p = 8.3 × 10−22). The maximum AUC achieved was 0.69 (CI95% = [0.66–0.71], p = 4.3 × 10−34) when cell-type proportion was included in the predictor

BB flavour tagging using charm decays at the LHCb experiment

An algorithm is described for tagging the flavour content at production of neutral $B$ mesons in the LHCb experiment. The algorithm exploits the correlation of the flavour of a $B$ meson with the charge of a reconstructed secondary charm hadron from the decay of the other $b$ hadron produced in the proton-proton collision. Charm hadron candidates are identified in a number of fully or partially reconstructed Cabibbo-favoured decay modes. The algorithm is calibrated on the self-tagged decay modes $B^+ \to J/\psi \, K^+$ and $B^0 \to J/\psi \, K^{*0}$ using $3.0\mathrm{\,fb}^{-1}$ of data collected by the LHCb experiment at $pp$ centre-of-mass energies of $7\mathrm{\,TeV}$ and $8\mathrm{\,TeV}$. Its tagging power on these samples of $B \to J/\psi \, X$ decays is $(0.30 \pm 0.01 \pm 0.01) \%$.Comment: All figures and tables, along with any supplementary material and additional information, are available at http://lhcbproject.web.cern.ch/lhcbproject/Publications/LHCbProjectPublic/LHCb-PAPER-2015-027.htm

Identification of beauty and charm quark jets at LHCb

Identification of jets originating from beauty and charm quarks is important for measuring Standard Model processes and for searching for new physics. The performance of algorithms developed to select $b$- and $c$-quark jets is measured using data recorded by LHCb from proton-proton collisions at $\sqrt{s}=7$ TeV in 2011 and at $\sqrt{s}=8$ TeV in 2012. The efficiency for identifying a $b(c)$ jet is about 65%(25%) with a probability for misidentifying a light-parton jet of 0.3% for jets with transverse momentum $p_{\rm T} > 20$ GeV and pseudorapidity $2.2 < \eta < 4.2$. The dependence of the performance on the $p_{\rm T}$ and $\eta$ of the jet is also measured

Search for B⁺c decays to the pp‾π⁺ final state

A search for the decays of the B + c meson to pp-π + is performed for the first time using a data sample corresponding to an integrated luminosity of 3.0 fb -1 collected by the LHCb experiment in pp collisions at centre-of-mass energies of 7 and 8 TeV. No signal is found and an upper limit, at 95% confidence level, is set, fcfu×B(B + c →ppπ + ) < 3.6×10-8 in the kinematic region m(pp) < 2.85 GeV/c2, p T (B) < 20 GeV/c and 2.0 < y(B) < 4.5, where B is the branching fraction and f c (f u ) is the fragmentation fraction of the b quark into a B c + (B + ) meson

Measurement of CP observables in B± → D(⁎)K± and B± → D(⁎)π± decays

Measurements of CP observables in B ± →D (⁎) K ± and B ± →D (⁎) π ± decays are presented, where D (⁎) indicates a neutral D or D ⁎ meson that is an admixture of D (⁎)0 and D¯ (⁎)0 states. Decays of the D ⁎ meson to the Dπ 0 and Dγ final states are partially reconstructed without inclusion of the neutral pion or photon, resulting in distinctive shapes in the B candidate invariant mass distribution. Decays of the D meson are fully reconstructed in the K ± π ∓ , K + K − and π + π − final states. The analysis uses a sample of charged B mesons produced in pp collisions collected by the LHCb experiment, corresponding to an integrated luminosity of 2.0, 1.0 and 2.0 fb −1 taken at centre-of-mass energies of s=7, 8 and 13 TeV, respectively. The study of B ± →D ⁎ K ± and B ± →D ⁎ π ± decays using a partial reconstruction method is the first of its kind, while the measurement of B ± →DK ± and B ± →Dπ ± decays is an update of previous LHCb measurements. The B ± →DK ± results are the most precise to date

Measurement of the track reconstruction efficiency at LHCb

The determination of track reconstruction efficiencies at LHCb using J/ψ→μ+μ- decays is presented. Efficiencies above 95% are found for the data taking periods in 2010, 2011, and 2012. The ratio of the track reconstruction efficiency of muons in data and simulation is compatible with unity and measured with an uncertainty of 0.8 % for data taking in 2010, and at a precision of 0.4 % for data taking in 2011 and 2012. For hadrons an additional 1.4 % uncertainty due to material interactions is assumed. This result is crucial for accurate cross section and branching fraction measurements in LHCb

Prompt K_short production in pp collisions at sqrt(s)=0.9 TeV

The production of K_short mesons in pp collisions at a centre-of-mass energy of 0.9 TeV is studied with the LHCb detector at the Large Hadron Collider. The luminosity of the analysed sample is determined using a novel technique, involving measurements of the beam currents, sizes and positions, and is found to be 6.8 +/- 1.0 microbarn^-1. The differential prompt K_short production cross-section is measured as a function of the K_short transverse momentum and rapidity in the region 0 < pT < 1.6 GeV/c and 2.5 < y < 4.0. The data are found to be in reasonable agreement with previous measurements and generator expectations.Comment: 6+18 pages, 6 figures, updated author lis

Observation of the decay B0s → ψ(2S)K +π−

The decay B0 s → ψ(2S)K +π− is observed using a data set corresponding to an integrated luminosity of 3.0 fb−1 collected by the LHCb experiment in pp collisions at centre-of-mass energies of 7 and 8 TeV. The branching fraction relative to the B0 → ψ(2S)K +π− decay mode is measured to be B(B0 s → ψ(2S)K +π−) B(B0 → ψ(2S)K +π−) = 5.38 ± 0.36 (stat) ± 0.22 (syst) ± 0.31 (f s/ fd)%, where f s/ fd indicates the uncertainty due to the ratio of probabilities for a b quark to hadronise into a B0 s or B0 meson. Using an amplitude analysis, the fraction of decays proceeding via an intermediate K∗(892)0 meson is measured to be 0.645 ± 0.049 (stat) ± 0.049 (syst) and its longitudinal polarisation fraction is 0.524 ± 0.056 (stat) ± 0.029 (syst). The relative branching fraction for this component is determined to be B(B0 s → ψ(2S)K∗(892)0) B(B0 → ψ(2S)K∗(892)0) = 5.58 ± 0.57 (stat) ± 0.40 (syst) ± 0.32 (f s/ fd)%. In addition, the mass splitting between the B0 s and B0 mesons is measured as M(B0 s ) − M(B0) = 87.45 ± 0.44 (stat) ± 0.09 (syst) MeV/c2