μSR at new accelerators

In this paper I speculate upon the potential of muon spin rotation/relaxation/resonance (μSR) for future refinement and/or exploitation at large accelerators like KAON, which might generate muon beams a hundred times more intense than today's best. Several schemes for efficient utilisation of such beams might be well worth implementing on existing muon channels. Work supported by NRC and NSERC.     

Are Two Metal Ions Better than One? Mono- and Binuclear α-Diimine-Re(CO)3 Complexes with Proton-Responsive Ligands in CO2 Reduction Catalysis

Here, the reduction chemistry of mono- and binuclear α-diimine-Re(CO)₃ complexes with proton responsive ligands and their application in the electrochemically-driven CO₂ reduction catalysis are presented. The work was aimed to investigate the impact of 1) two metal ions in close proximity and 2) an internal proton source on catalysis. Therefore, three different Re complexes, a binuclear one with a central phenol unit, 3 , and two mononuclear, one having a central phenol unit, 1 , and one with a methoxy unit, 2 , were utilised. All complexes are active in the CO₂-to-CO conversion and CO is always the major product. The catalytic rate constant k_cat for all three complexes is much higher and the overpotential is lower in DMF/water mixtures than in pure DMF (DMF=N,N-dimethylformamide). Cyclic voltammetry (CV) studies in the absence of substrate revealed that this is due to an accelerated chloride ion loss after initial reduction in DMF/water mixtures in comparison to pure DMF. Chloride ion loss is necessary for subsequent CO₂ binding and this step is around ten times faster in the presence of water [ 2 : k^Cl(DMF)≈1.7 s⁻¹; k^Cl(DMF/H₂O)≈20 s⁻¹]. The binuclear complex 3 with a proton responsive phenol unit is more active than the mononuclear complexes. In the presence of water, the observed rate constant k_obs for 3 is four times higher than of 2 , in the absence of water even ten times. Thus, the two metal centres are beneficial for catalysis. Lastly, the investigation showed that the phenol unit has no impact on the rate of the catalysis, it even slows down the CO₂-to-CO conversion. This is due to an unproductive, competitive side reaction: After initial reduction, 1 and 3 loose either Cl⁻ or undergo a reductive OH deprotonation forming a phenolate unit. The phenolate could bind to the metal centre blocking the sixth coordination site for CO₂ activation. In DMF, O−H bond breaking and Cl⁻ ion loss have similar rate constants [ 1 : k^Cl(DMF)≈2 s⁻¹, k^OH≈1.5 s⁻¹], in water/DMF Cl⁻ loss is much faster. Thus, the effect on the catalytic rate is more pronounced in DMF. However, the acidic protons lower the overpotential of the catalysis by about 150 mV.     

Elucidation of the kijanimicin gene cluster: insights into the biosynthesis of spirotetronate antibiotics and nitrosugars

The antibiotic kijanimicin produced by the actinomycete Actinomadura kijaniata has a broad spectrum of bioactivities as well as a number of interesting biosynthetic features. To understand the molecular basis for its formation and to develop a combinatorial biosynthetic system for this class of compounds, a 107.6 kb segment of the A. kijaniata chromosome containing the kijanimicin biosynthetic locus was identified, cloned, and sequenced. The complete pathway for the formation of TDP-l-digitoxose, one of the two sugar donors used in construction of kijanimicin, was elucidated through biochemical analysis of four enzymes encoded in the gene cluster. Sequence analysis indicates that the aglycone kijanolide is formed by the combined action of a modular Type-I polyketide synthase, a conserved set of enzymes involved in formation, attachment, and intramolecular cyclization of a glycerate-derived three-carbon unit, which forms the core of the spirotetronate moiety. The genes involved in the biosynthesis of the unusual deoxysugar d-kijanose [2,3,4,6-tetradeoxy-4-(methylcarbamyl)-3-C-methyl-3-nitro-d-xylo-hexopyranose], including one encoding a flavoenzyme predicted to catalyze the formation of the nitro group, have also been identified. This work has implications for the biosynthesis of other spirotetronate antibiotics and nitrosugar-bearing natural products, as well as for future mechanistic and biosynthetic engineering efforts.     

Pt@MOF-177: synthesis, room-temperature hydrogen storage and oxidation catalysis

The gas-phase loading of [Zn(4)O(btb)(2)](8) (MOF-177; H(3)btb=1,3,5-benzenetribenzoic acid) with the volatile platinum precursor [Me(3)PtCp'] (Cp'=methylcyclopentadienyl) was confirmed by solid state (13)C magic angle spinning (MAS)-NMR spectroscopy. Subsequent reduction of the inclusion compound [Me(3)PtCp'](4)@MOF-177 by hydrogen at 100 bar and 100 degrees C for 24 h was carried out and gave rise to the formation of platinum nanoparticles in a size regime of 2-5 nm embedded in the unchanged MOF-177 host lattice as confirmed by transmission electron microscopy (TEM) micrographs and powder X-ray diffraction (PXRD). The room-temperature hydrogen adsorption of Pt@MOF-177 has been followed in a gravimetric fashion (magnetic suspension balance) and shows almost 2.5 wt % in the first cycle, but is decreased down to 0.5 wt % in consecutive cycles. The catalytic activity of Pt@MOF-177 towards the solvent- and base-free room temperature oxidation of alcohols in air has been tested and shows Pt@MOF-177 to be an efficient catalyst in the oxidation of alcohols.     

Synthesis,Crystal Structures,and Properties of the Copper(I) Halide Coordination Polymers 2[CuX(μ‐2‐chloropyrazine‐N,N')] (X = Cl,Br), 1[CuI(2‐chloropyrazine‐N)], and [Cu2I2(2‐chloropyrazine)]

The new copper coordination polymers 2[CuX(μ‐2‐chlor‐opyrazine‐N, N')] (X = Cl ( I ), Br ( II ), 1[CuI(2‐chloropyrazine‐N)] ( III ) and [Cu₂I₂(2‐chloropyrazine)] ( IV ) has been prepared by the reaction of the copper(I) halides with 2‐chloropyrazine at roomtemperature or under hydrothermal conditions. The crystal structures of the 1:1 compounds I and II consist of zig‐zag CuX single chains running parallel to the crystallographic a‐axis which are linked by the 2‐chloropyrazine spacer molecules to sheets parallel to (010). For the iodine compound III a one‐dimensional structure is found which consists of CuX double chains running parallel to the crystallographic a‐axis. The thermic properties of all compounds were investigated in different gas atmospheres using simultaneously differential thermal analysis and thermogravimetry (DTA‐TG) as well as temperature resolved X‐ray powder diffraction. On heating, the 1:1 compounds I and II decompose directly to the corresponding copper(I) Halides, whereas the thermal decomposition of III occcur via IV as an intermediate.     

Muonium in bulk fused quartz: Test case for RAHD relaxation theory

Muonium (μ ⁺ e ⁻) in bulk fused quartz is a unique system in that theμ ⁺ spin polarization (in the muonium state) relaxes almost entirely via random anisotropic hyperfine distortions (RAHD). As such, this system provides an excellent test case for a new RAHD spin relaxation theory. This theory is quantitatively compared to static zero field data and the functional characteristics in both the high field and dynamic limits are considered as well.