Preparation of a Semiquinonate-Bridged Diiron(II) Complex and Elucidation of its Geometric and Electronic Structures

The synthesis and crystal structure of a diiron(II) complex containing a bridging semiquinonate radical are presented. The unique electronic structure of this S = 7/2 complex is examined with spectroscopic (absorption, EPR, resonance Raman) and computational methods

Synthesis and Spectroscopic Characterization of High-Spin Mononuclear Iron(II) \u3cem\u3ep\u3c/em\u3e-Semiquinonate Complexes

Two mononuclear iron(II) p-semiquinonate (pSQ) complexes have been generated via one-electron reduction of precursor complexes containing a substituted 1,4-naphthoquinone ligand. Detailed spectroscopic and computational analysis confirmed the presence of a coordinated pSQ radical ferromagnetically coupled to the high-spin FeII center. The complexes are intended to model electronic interactions between (semi)quinone and iron cofactors in biology

Postgraduate nurses’ insights into the nursing leadership role. Do they intuitively link the role to patient safety?

Nursing leaders are compelled to ensure a safety and quality agenda in the acute care environment as patient outcomes are linked to nursing care. Good nursing leadership where focus is directed to accountability and responsibility for clinical outcomes and patient safety, results in reduced adverse events and patient mortality. Integral to the future of high-quality effective clinical care with an absence of errors is the training of the next generation of nursing leaders. In this discussion paper, the extent to which future nurse leaders intuitively acknowledge patient safety as part of their leadership role was examined amongst a cohort of postgraduate nursing students. A content analysis to search for quality and safety terminology was conducted on 146 essay responses to a question about the nurse leader role in today’s healthcare environment. The results indicated minimal acknowledgement of patient safety as an intuitive consideration in the nursing leadership role. Recommendations are discussed for developing postgraduate nursing educational curricula with patient safety strategies as a central component to the practice of leadership

Unit Killing Vector Fields on Nearly Kahler Manifolds

We study 6-dimensional nearly Kahler manifolds admitting a Killing vector field of unit length. In the compact case it is shown that up to a finite cover there is only one geometry possible, that of the 3--symmetric space $S^3 \times S^3$

Cycles in the chamber homology of GL(3)

Let F be a nonarchimedean local field and let GL(N) = GL(N,F). We prove the existence of parahoric types for GL(N). We construct representative cycles in all the homology classes of the chamber homology of GL(3).Comment: 45 pages. v3: minor correction

Matrix elements of the electromagnetic operator between kaon and pion states

We compute the matrix elements of the electromagnetic (EM) operator between kaon and pion states, using lattice QCD with maximally twisted-mass fermions and two flavors of dynamical quarks (Nf = 2). The EM operator is renormalized non-perturbatively in the RI'/MOM scheme and our simulations cover pion masses as light as 260 MeV and three values of the lattice spacing, ranging from ~ 0.07 up to ~ 0.1 fm. At the physical point our preliminary result for the K -> pion tensor form factor at zero-momentum transfer is fT[K\pi](0) = 0.42(2_stat), which differs significantly from the old quenched result fT[K\pi](0) = 0.78(6) obtained by the SPQcdR Collaboration with pion masses above 500 MeV. We investigate the source of this difference and conclude that it is mainly related to the chiral extrapolation of the quenched data. For the case of the tensor charge of the pion we obtain the preliminary value fT[\pi\pi](0) = 0.200(14_stat), which can be compared with the result fT[\pi\pi](0) = 0.216(34) obtained at Nf = 2 by the QCDSF Collaboration using higher pion masses.Comment: 7 pages, 5 figures, contribution to the XXVIII International Symposium on Lattice Field Theory, Lattice2010, June 14-19, 2010, Villasimius, Ital

Mononuclear Iron-(hydro/semi)quinonate Complexes Featuring Neutral and Charged Scorpionates: Synthetic Models of Intermediates in the Hydroquinone Dioxygenase Mechanism

Neutral and anionic scorpionate ligands have been employed to generate active-site models of hydroquinone dioxygenases (HQDOs). While the nonheme Fe center in nearly all HQDOs is coordinated to one Asp (or Glu) and two His residues, 1,2-gentisate dioxygenase (GDO) is unique in featuring a three His triad instead. A synthetic GDO model was therefore prepared with the neutral tris(4,5-diphenyl-1-methylimidazol-2-yl)phosphine (Ph2TIP) ligand. The gentisate substrate was mimicked with the bidentate ligand 2-(1-methylbenzimidazol-2-yl)hydroquinonate (BIHQ). X-ray diffraction analysis of the resulting complex, [Fe(Ph2TIP)(BIHQ)]OTf (1a), revealed a distorted square-pyramidal geometry. Structural and electrochemical data collected for 1a were compared to those previously reported for [Fe(Ph2Tp)(BIHQ)] (1b), which features an anionic hydridotris(3,5-diphenylpyrazol-1-yl)borate (Ph2Tp) ligand. Oxidation of 1a and 1b provides the corresponding FeIII complexes (2a/2b) and the crystal structure of 2b is reported. Both complexes undergo reversible deprotonation to yield the brown chromophores, 3a and 3b. Detailed studies of 3a and 3b with spectroscopic (UV/Vis absorption, EPR, resonance Raman) and computational methods determined that each complex consists of a high-spin FeII center ferromagnetically coupled to a p-semiquinonate radical (BISQ). The (de)protonation-induced valence tautomerization described here resembles key steps in the putative HQDO mechanism