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A three-hour workshop on earthquake science-to-practice was held in Wellington, New Zealand on 26 April 2017. The objective was to provide a forum to discuss the contribution of earthquake science and engineering to decision-making (with a focus on policy). Over 40 people attended, from disciplines that included earthquake science, structural engineering, engineering geology, social science, and economics; and relevant sectors such as emergency management, policy (at local, regional and central government levels), consultancies, and insurance. The workshop provided a useful forum for getting people together to discuss science-to-practice issues and opportunities. It allowed participants to think more broadly about potential barriers (i.e. from communication through to collaboration), and consider how people can work together better within current decision-making environments. There is considerable scope for future initiatives of this kind, which raise awareness, broaden perspectives and build relationships to support future decision-making.

© 2015 John Wiley & Sons, Ltd. The hepatitis C virus (HCV) infects more than 180 million people worldwide, with long-term consequences including liver failure and hepatocellular carcinoma. Quercetin bioflavonoids can decrease HCV production in tissue culture, in part through inhibition of heat shock proteins. If quercetin demonstrates safety and antiviral activity in patients, then it could be developed into an inexpensive HCV treatment for third world countries or other affected populations that lack financial means to cover the cost of mainstream antivirals. A phase 1 dose escalation study was performed to evaluate the safety of quercetin in 30 untreated patients with chronic HCV infection and to preliminarily characterize quercetin's potential in suppressing viral load and/or liver injury. Quercetin displayed safety in all trial participants. Additionally, 8 patients showed a "clinically meaningful" 0.41-log viral load decrease. There was a positive correlation (r = 0.41, p = 0.03) indicating a tendency for HCV decrease in patients with a lower ratio of plasma quercetin relative to dose. No significant changes in aspartate transaminase and alanine transaminase were detected. In conclusion, quercetin exhibited safety (up to 5 g daily) and there was a potential for antiviral activity in some hepatitis C patients.

The structural and physicochemical properties of the manganese-corrolazine (Cz) complexes (TBP8Cz)Mn(V)O (1) and (TBP8Cz)Mn(III) (2) (TBP = p-tert-butylphenyl) have been determined. Recrystallization of 2 from toluene/MeOH resulted in the crystal structure of (TBP8Cz)Mn(III)(CH3OH) (2 x MeOH). The packing diagram of 2 x MeOH reveals hydrogen bonds between MeOH axial ligands and meso N atoms of adjacent molecules. Solution binding studies of 2 with different axial ligands (Cl-, Et3PO, and Ph3PO) reveal strong binding, corroborating the preference of the Mn(III) ion for a five-coordinate environment. High-frequency and field electron paramagnetic resonance (HFEPR) spectroscopy of solid 2 x MeOH shows that 2 x MeOH is best described as a high-spin (S = 2) Mn(III) complex with zero-field splitting parameters typical of corroles. Structural information on 1 was obtained through an X-ray absorption near-edge structure (XANES)/extended X-ray absorption fine structure (EXAFS) study and compared to XANES/EXAFS data for 2 x MeOH. The XANES data for 1 shows an intense pre-edge transition characteristic of a high-valent metal-oxo species, and a best fit of the EXAFS data gives a short Mn-O bond distance of 1.56 A, confirming the structure of the metal-oxo unit in 1. Detailed spectroelectrochemical studies of 1 and 2 were performed revealing multiple reversible redox processes for both complexes, including a relatively low potential for the Mn(V) --Mn(IV) process in 1 (near 0.0 V vs saturated calomel reference electrode). Chemical reduction of 1 results in the formation of a Mn(III)Mn(IV)(mu-O) dimer as characterized by electron paramagnetic resonance spectroscopy.

The reaction between (TBP)8(Cz)Mn(III) (1) and the oxygen atom donors iodosylbenzene (PhIO) or p-cyanodimethylaniline-N-oxide (CDMANO) leads to the manganese(V)−oxo complex (TBP)8(Cz)Mn(V)⋮O (2), which has been isolated and characterized previously. Under catalytic conditions with 1 as added catalyst and PhIO as oxidant, both sulfoxidation of PhSMe and epoxidation of cis-stilbene is observed, whereas with CDMANO no sulfoxidation takes place, suggesting that 2 is not the active oxidant. Examination of the independent reactivity of isolated 2 toward PhSMe and cis-stilbene supports this conclusion. A mechanism which relies on a novel type of oxidant involving Lewis acid activation of PhIO by the Mn(V)−oxo complex 2 accounts for these observations and is confirmed by 18O-labeling experiments.

The four-coordinate Ni(+) complex [PhTt(t)(Bu)]Ni(I)CO, where PhTt(t)()(Bu) = phenyltris((tert-buthylthio)methyl)borate (a tridentate thioether donor ligand), serves as a possible model for key Ni-CO reaction intermediates in the acetyl-CoA synthase (ACS) catalytic cycle. Resonance Raman, electronic absorption, magnetic circular dichroism (MCD), variable-temperature variable-field MCD, and electron paramagnetic resonance spectroscopies were utilized in conjunction with density functional theory and semiemperical INDO/S-CI calculations to investigate the ground and excited states of [PhTt(t)()(Bu)]Ni(I)CO. These studies reveal extensive Ni(+) --> CO pi-back-bonding interactions, as evidenced by a low C-O stretching frequency (1995 cm(-)(1)), a calculated C-O stretching force constant of 15.5 mdyn/A (as compared to k(CO)(free CO) = 18.7 mdyn/A), and strong Ni(+) --> CO charge-transfer absorption intensities. Calculations reveal that this high degree of pi-back-bonding is due to the fact that the Ni(+) 3d orbitals are in close energetic proximity to the CO pi acceptor orbitals. In the ACS "paramagnetic catalytic cycle", the high degree of pi-back-bonding in the putative Ni(+)-CO intermediate (the NiFeC species) is not expected to preclude methyl transfer from CH(3)-CoFeSP.

Spectroscopic and density functional theory (DFT) electronic structure computational studies on a binuclear bis-mu-oxo bridged (Ni(3+))(2) complex, [(PhTt(t(Bu))(2)Ni(2)(mu-O)(2)] (1), where (PhTt(t(Bu)) represents phenyl-tris((tert-butylthio)methyl)borate, are presented and discussed. These studies afford a detailed description of the Ni(2)O(2) core electronic structure in bis-mu-oxo (Ni(3+))(2) dimers and provide insight into the possible role of the (PhTt(t(Bu)) thioether ligand in the formation of 1 from a Ni(1+) precursor by O(2) activation. From a normal coordinate analysis of resonance Raman data, a value of k(Ni)(-)(O) = 2.64 mdyn/A is obtained for the Ni-O stretch force constant for 1. This value is smaller than k(Cu)(-)(O) = 2.82-2.90 mdyn/A obtained for bis-mu-oxo (Cu(3+))(2) dimers possessing nitrogen donor ligands, indicating a reduced metal-oxo bond strength in 1. Electronic absorption and magnetic circular dichroism spectroscopic techniques permit identification of several O-->Ni and S-->Ni charge transfer (CT) transitions that are assigned on the basis of DFT calculations. The dominant O-->Ni CT transition of 1 occurs at 17 700 cm(-)(1), red-shifted by approximately 7000 cm(-)(1) relative to the corresponding transition in bis-mu-oxo (Ni(3+))(2) dimers with nitrogen donor ligands. This red-shift along with the relatively low value of k(Ni)(-)(O) are due primarily to the presence of the thioether ligands in 1 that greatly affect the compositions of the Ni(2)O(2) core MOs. This unique property of the thioether ligand likely contributes to the reactivity of the Ni center in the precursor [(PhTt(t(Bu))Ni(1+)CO] toward O(2). DFT computations reveal that conversion of a hypothetical side-on peroxo (Ni(2+))(2) dimer, [(PhTt(t(Bu))(2)Ni(2)(mu-eta(2):eta(2)-O(2))], to the bis-mu-oxo (Ni(3+))(2) dimer 1 is energetically favorable by 32 kcal/mol and occurs without a significant activation energy barrier (DeltaH++) = 2 kcal/mol).

The synthesis and characterization of an oxomanganese(V) corrolazine, (TBP)8(Cz)Mn(V)O (2), are reported. This remarkably stable high-valent complex is obtained from the stoichiometric reaction of (TBP)8(Cz)Mn(III) (1) with m-CPBA and is easily purified by standard chromatographic methods on silica gel at room temperature. Complex 2 exhibits a diamagnetic 1H NMR spectrum indicative of a low-spin d2 Mn(V)O species. LDI-TOFMS of 2 shows the predicted isotopic envelope at m/z 1426.8. This envelope shifts to higher mass as expected after the facile exchange of the terminal oxo group with H218O. The resonance Raman spectrum of 2 either in solution or in the solid state shows a strongly enhanced Raman band for the stretching mode of the Mn-oxo bond, which also shifts as expected upon 18O substitution: 2(16O), 979 cm-1; 2(18O), 938 cm-1 (in CH2Cl2). Initial reactivity studies show that 2 rapidly transfers the terminal oxo ligand to PPh3, resulting in the quantitative formation of OPPh3 and concomitant reduction of 2 back to 1. Complex 2 is the first example of an oxomanganese(V)-porphyrinoid complex that can be isolated at room temperature.

The potential of 1s2p resonant inelastic (Raman) X-ray scattering (RIXS) is demonstrated for a series of Ni coordination complexes. In this technique, incident and scattered photon energies lie in the hard X-ray range (>5 keV). The 1s2p RIXS contour plots provide information that is complementary to K-edge and L-edge spectroscopy. RIXS spectroscopy promises to be a valuable probe of electronic structure