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

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

Planting Date, Hybrid Maturity, and Weather Effects on Maize Yield and Crop Stage

Unfavorable weather conditions frequently cause farmers to plant maize (Zea mays L.) outside the optimum planting timeframe. We analyzed maize yield and phenology from a multilocation, year, hybrid relative maturity, and planting date experiment performed in Iowa, USA. Our objectives were to determine the optimum combination of planting date and relative maturity to maximize maize grain yield per environment and to elucidate the risk associated with the use of “full-season hybrids” when planting occurs beyond the optimum planting date. Analysis of variance (ANOVA) attributed 70% of the variability in grain yield to planting date and only 10% to relative maturity indicating that short and full-season hybrid relative maturities produced similar grain yields regardless of when they were planted as long as the crops reached maturity before harvesting. Our analysis indicated time to silking is a good indication of expected yield potential with a critical time (beyond which yield is reduced) to be 23 July for Iowa. Furthermore, we found that a minimum growing degree accumulation of 648°Cday during the grain-filling period maximized maize yield. Overall, this study brings new results to assist decision making regarding planting date by hybrid relative maturity across Iowa

The multiple quantum NMR dynamics in systems of equivalent spins with the dipolar ordered initial state

The multiple quantum (MQ) NMR dynamics in the system of equivalent spins with the dipolar ordered initial state is considered. The high symmetry of the MQ Hamiltonian is used in order to develop the analytical and numerical methods for an investigation of the MQ NMR dynamics in the systems consisting of hundreds of spins from "the first principles". We obtain the dependence of the intensities of the MQ NMR coherences on their orders (profiles of the MQ NMR coherences) for the systems of $200 - 600$ spins. It is shown that these profiles may be well approximated by the exponential distribution functions. We also compare the MQ NMR dynamics in the systems of equivalent spins having two different initial states, namely the dipolar ordered state and the thermal equilibrium state in the strong external magnetic field.Comment: 11 pages 4 figure

Uniformization and an Index Theorem for Elliptic Operators Associated with Diffeomorphisms of a Manifold

We consider the index problem for a wide class of nonlocal elliptic operators on a smooth closed manifold, namely differential operators with shifts induced by the action of an isometric diffeomorphism. The key to the solution is the method of uniformization: We assign to the nonlocal problem a pseudodifferential operator with the same index, acting in sections of an infinite-dimensional vector bundle on a compact manifold. We then determine the index in terms of topological invariants of the symbol, using the Atiyah-Singer index theorem.Comment: 16 pages, no figure

Learning from Minimum Entropy Queries in a Large Committee Machine

In supervised learning, the redundancy contained in random examples can be avoided by learning from queries. Using statistical mechanics, we study learning from minimum entropy queries in a large tree-committee machine. The generalization error decreases exponentially with the number of training examples, providing a significant improvement over the algebraic decay for random examples. The connection between entropy and generalization error in multi-layer networks is discussed, and a computationally cheap algorithm for constructing queries is suggested and analysed.Comment: 4 pages, REVTeX, multicol, epsf, two postscript figures. To appear in Physical Review E (Rapid Communications

Holomorphic Supercurves and Supersymmetric Sigma Models

We introduce a natural generalisation of holomorphic curves to morphisms of supermanifolds, referred to as holomorphic supercurves. More precisely, supercurves are morphisms from a Riemann surface, endowed with the structure of a supermanifold which is induced by a holomorphic line bundle, to an ordinary almost complex manifold. They are called holomorphic if a generalised Cauchy-Riemann condition is satisfied. We show, by means of an action identity, that holomorphic supercurves are special extrema of a supersymmetric action functional.Comment: 30 page

The Selberg trace formula for Dirac operators

We examine spectra of Dirac operators on compact hyperbolic surfaces. Particular attention is devoted to symmetry considerations, leading to non-trivial multiplicities of eigenvalues. The relation to spectra of Maass-Laplace operators is also exploited. Our main result is a Selberg trace formula for Dirac operators on hyperbolic surfaces