Facile O-atom insertion into C-C and C-H bonds by a trinuclear copper complex designed to harness a singlet oxene

Two trinuclear copper [CuICuICuI(L)]1+ complexes have been prepared with the multidentate ligands (L) 3,3'-(1,4-diazepane-1,4-diyl)bis(1-((2-(dimethylamino)ethyl)(methyl)amino)propan-2-ol) (7-Me) and (3,3'-(1,4-diazepane-1,4-diyl)bis(1-((2-(diethylamino) ethyl)(ethyl) amino)propan-2-ol) (7-Et) as models for the active site of the particulate methane monooxygenase (pMMO). The ligands were designed to form the proper spatial and electronic geometry to harness a "singlet oxene," according to the mechanism previously suggested by our laboratory. Consistent with the design strategy, both [CuICuICuI(L)]1+ reacted with dioxygen to form a putative bis(µ3-oxo)CuIICuIICuIII species, capable of facile O-atom insertion across the central C-C bond of benzil and 2,3-butanedione at ambient temperature and pressure. These complexes also catalyze facile O-atom transfer to the C-H bond of CH3CN to form glycolonitrile. These results, together with our recent biochemical studies on pMMO, provide support for our hypothesis that the hydroxylation site of pMMO contains a trinuclear copper cluster that mediates C-H bond activation by a singlet oxene mechanism

CMB Constraint on Radion Evolution in the Brane World Scenario

In many versions of brane model, the modulus field of extra dimensions, the radion, could have cosmological evolution, which induces variation of the Higgs vacuum expectation value, , resulting in cosmological variation of the electron mass $m_e$. The formation of Cosmic Microwave Background (CMB) anisotropies is thus affected, causing changes both in the peaks positions and amplitudes in the CMB power spectra. Using the three-year Wilkinson Microwave Anisotropies Probe (WMAP) CMB data, with the Hubble parameter $H_0$ fixed to be the Hubble Space Telescope (HST) result 72 km s$^{-1}$ Mpc$^{-1}$, we obtain a constraint on $\rho$, the ratio of the value of at CMB recombination to its present value, to be [0.97, 1.02].Comment: 7 pages, 6 figures, minor changes of format to conform with PRD forma

Investigation of Settlements of a Trunk Road Embankment in Hong Kong

A 25 m high fill embankment was constructed as part of a Trunk Road scheme in Hong Kong. In June 1985, large settlements of the order of 250 mm were observed in the embankment. This was followed by a local slippage of surface material from the downstream slope face. To meet the schedule for opening the trunk road in late September, a number of emergency measures costing about HK$1 M (US$0.13 M) were implemented to stabilize the embankment. An investigation was subsequently carried out to assess the cause of the movement and the long term stability of the embankment. This paper summarizes the sequence of events leading to the settlements and outlines the investigation carried out. The proposed hydrocompaction mechanism and the effects of grouting on the embankment are discussed

Cosmic ray feedback in the FIRE simulations: constraining cosmic ray propagation with GeV gamma ray emission

We present the implementation and the first results of cosmic ray (CR) feedback in the Feedback In Realistic Environments (FIRE) simulations. We investigate CR feedback in non-cosmological simulations of dwarf, sub-$L\star$ starburst, and $L\star$ galaxies with different propagation models, including advection, isotropic and anisotropic diffusion, and streaming along field lines with different transport coefficients. We simulate CR diffusion and streaming simultaneously in galaxies with high resolution, using a two moment method. We forward-model and compare to observations of $\gamma$-ray emission from nearby and starburst galaxies. We reproduce the $\gamma$-ray observations of dwarf and $L\star$ galaxies with constant isotropic diffusion coefficient $\kappa \sim 3\times 10^{29}\,{\rm cm^{2}\,s^{-1}}$. Advection-only and streaming-only models produce order-of-magnitude too large $\gamma$-ray luminosities in dwarf and $L\star$ galaxies. We show that in models that match the $\gamma$-ray observations, most CRs escape low-gas-density galaxies (e.g.\ dwarfs) before significant collisional losses, while starburst galaxies are CR proton calorimeters. While adiabatic losses can be significant, they occur only after CRs escape galaxies, so they are only of secondary importance for $\gamma$-ray emissivities. Models where CRs are ``trapped'' in the star-forming disk have lower star formation efficiency, but these models are ruled out by $\gamma$-ray observations. For models with constant $\kappa$ that match the $\gamma$-ray observations, CRs form extended halos with scale heights of several kpc to several tens of kpc.Comment: 31 pages, 26 figures, accepted for publication in MNRA

Application of titanium-in-quartz thermobarometry to greenschist facies veins and recrystallized quartzites in the Hsüehshan range, Taiwan

The accuracy, reliability and best practises of Ti-in-quartz thermobarometry (TitaniQ) in greenschist facies rocks have not been established. To address these issues, we measured Ti concentrations in rutile-bearing samples of moderately deformed, partially recrystallized quartzite and vein quartz from the Hsüehshan range, Taiwan. The spread of Ti concentrations of recrystallized grains in quartzite correlates with recrystallized grain size. Recrystallized quartz (grain size ~100–200 μm) that formed during early deformation within the biotite stability field shows a marked increase in intermediate Ti-concentration grains (~1–10 ppm) relative to detrital porphyroclasts (Ti ~0.1–200 ppm). Fine recrystallized quartz (~5% of the samples by area, grain size ~10–20 μm) has a further restricted Ti concentration peaking at 0.8–2 ppm. This trend suggests equilibration of Ti in recrystallized quartz with a matrix phase during deformation and cooling. Unlike previously documented examples, Ti concentration in the quartzite is inversely correlated with blue cathodoluminescence. Deformation was associated with a minimum grain boundary diffusivity of Ti on the order of 10^(−22)m^2 s^(−1). Vein emplacement and quartzite recrystallization are independently shown to have occurred at 250–350 °C and 300–410 °C, respectively, with lithostatic pressure of 3–4 kbar (assuming a geothermal gradient of 25° km^(−1)), and with hydrostatic fluid pressure. Estimates of the accuracy of TitaniQ at these conditions depend on whether lithostatic or fluid pressure is used in the TitaniQ calibration. Using lithostatic pressure and these temperatures, the Thomas et al. (2010) calibration yields Ti concentrations within error of concentrations measured by SIMS. If fluid pressure is instead used, predicted temperatures are ~30–40 °C too low. TitaniQ has potential to yield accurate PT information for vein emplacement and dynamic recrystallization of quartz at temperatures as low as ~250 °C, however clarification of the relevant pressure term and further tests in rutile-present rocks are warranted

Unique gap structure and symmetry of the charge density wave in single-layer VSe2_2

Single layers of transition metal dichalcogenides (TMDCs) are excellent candidates for electronic applications beyond the graphene platform; many of them exhibit novel properties including charge density waves (CDWs) and magnetic ordering. CDWs in these single layers are generally a planar projection of the corresponding bulk CDWs because of the quasi-two-dimensional nature of TMDCs; a different CDW symmetry is unexpected. We report herein the successful creation of pristine single-layer VSe$_2$, which shows a ($\sqrt7 \times \sqrt3$) CDW in contrast to the (4 $\times$ 4) CDW for the layers in bulk VSe$_2$. Angle-resolved photoemission spectroscopy (ARPES) from the single layer shows a sizable ($\sqrt7 \times \sqrt3$) CDW gap of $\sim$100 meV at the zone boundary, a 220 K CDW transition temperature twice the bulk value, and no ferromagnetic exchange splitting as predicted by theory. This robust CDW with an exotic broken symmetry as the ground state is explained via a first-principles analysis. The results illustrate a unique CDW phenomenon in the two-dimensional limit