Results are presented from searches for the standard model Higgs boson in proton-proton collisions at root s = 7 and 8 TeV in the Compact Muon Solenoid experiment at the LHC, using data samples corresponding to integrated luminosities of up to 5.1 fb(-1) at 7 TeV and 5.3 fb(-1) at 8 TeV. The search is performed in five decay modes: gamma gamma, ZZ, W+W-, tau(+)tau(-), and b (b) over bar. An excess of events is observed above the expected background, with a local significance of 5.0 standard deviations, at a mass near 125 GeV, signalling the production of a new particle. The expected significance for a standard model Higgs boson of that mass is 5.8 standard deviations. The excess is most significant in the two decay modes with the best mass resolution, gamma gamma and ZZ; a fit to these signals gives a mass of 125.3 +/- 0.4(stat.) +/- 0.5(syst.) GeV. The decay to two photons indicates that the new particle is a boson with spin different from one. (C) 2012 CERN. Published by Elsevier B.V. All rights reserved
Exceptionally high peroxidase-like and catalase-like activities of iron(III)-TAML activators of H 2O 2 ( 1: Tetra-Amidato-Macrocyclic-Ligand Fe (III) complexes [ F e{1,2-X 2C 6H 2-4,5-( NCOCMe 2 NCO) 2CR 2}(OH 2)] (-)) are reported from pH 6-12.4 and 25-45 degrees C. Oxidation of the cyclometalated 2-phenylpyridine organometallic complex, [Ru (II)( o-C 6H 4py)(phen) 2]PF 6 ( 2) or "ruthenium dye", occurs via the equation [ Ru II ] + 1/2 H 2 O 2 + H +-->(Fe III - TAML) [ Ru III ] + H 2 O, following a simple rate law rate = k obs (per)[ 1][H 2O 2], that is, the rate is independent of the concentration of 2 at all pHs and temperatures studied. The kinetics of the catalase-like activity (H 2 O 2 -->(Fe III - TAML) H 2 O + 1/2 O 2) obeys a similar rate law: rate = k obs (cat)[ 1][H 2O 2]). The rate constants, k obs (per) and k obs (cat), are strongly and similarly pH dependent, with a maximum around pH 10. Both bell-shaped pH profiles are quantitatively accounted for in terms of a common mechanism based on the known speciation of 1 and H 2O 2 in this pH range. Complexes 1 exist as axial diaqua species [FeL(H 2O) 2] (-) ( 1 aqua) which are deprotonated to afford [FeL(OH)(H 2O)] (2-) ( 1 OH) at pH 9-10. The pathways 1 aqua + H 2O 2 ( k 1), 1 OH + H 2O 2 ( k 2), and 1 OH + HO 2 (-) ( k 4) afford one or more oxidized Fe-TAML species that further rapidly oxidize the dye (peroxidase-like activity) or a second H 2O 2 molecule (catalase-like activity). This mechanism is supported by the observations that (i) the catalase-like activity of 1 is controllably retarded by addition of reducing agents into solution and (ii) second order kinetics in H 2O 2 has been observed when the rate of O 2 evolution was monitored in the presence of added reducing agents. The performances of the 1 complexes in catalyzing H 2O 2 oxidations are shown to compare favorably with the peroxidases further establishing Fe (III)-TAML activators as miniaturized enzyme replicas with the potential to greatly expand the technological utility of hydrogen peroxide.
The reaction between an Fe(III) complex and O(2) to afford a stable catalytically active diiron(IV)-mu-oxo compound is described. Phosphonium salts of orange five-coordinated Fe(III)-TAML complexes with an axial aqua ligand ([PPh(4)]1-H(2)O, tetraamidato macrocyclic Fe(III) species derived from 3,3,6,6,9,9-hexamethyl-3,4,8,9-tetrahydro-1H-1,4,8,11-benzotetraazacyclotridecine-2,5,7,10(6H,11H)-tetraone) react rapidly with O(2) in CH(2)Cl(2) or other weakly coordinating solvents to produce black mu-oxo-bridged diiron(IV) complexes, 2, in high yields. Complexes 2 have been characterized by X-ray crystallography (2 cases), microanalytical data, mass spectrometry, UV/Vis, Mossbauer, and (1)H NMR spectroscopies. Mossbauer data show that the diamagnetic Fe-O-Fe unit contains antiferromagnetically coupled S = 1 Fe(IV) sites; diamagnetic (1)H NMR spectra are observed. The oxidation of PPh(3) to OPPh(3) by 2 was confirmed by UV/Vis and GC-MS. Labeling experiments with (18)O(2) and H(2)(18)O established that the bridging oxygen atom of 2 derives from O(2). Complexes 2 catalyze the selective oxidation of benzylic alcohols into the corresponding aldehydes and bleach rapidly organic dyes, such as Orange II in MeCN-H(2)O mixtures; reactivity evidence suggests that free radical autoxidation is not involved. This work highlights a promising development for the advancement of green oxidation technology, as O(2) is an abundant, clean, and inexpensive oxidizing agent.
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