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

IMPLICATIONS OF FEEDER PIG PRICE VARIABILITY IN VIRGINIA TELE-AUCTION MARKETS

Demand and Price Analysis,

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

Structural, Spectroscopic, and Electrochemical Properties of Nonheme Fe(II)-Hydroquinonate Complexes: Synthetic Models of Hydroquinone Dioxygenases

Using the tris(3,5-diphenylpyrazol-1-yl)borate (Ph2Tp) supporting ligand, a series of mono- and dinuclear ferrous complexes containing hydroquinonate (HQate) ligands have been prepared and structurally characterized with X-ray crystallography. The monoiron(II) complexes serve as faithful mimics of the substrate-bound form of hydroquinone dioxygenases (HQDOs) – a family of nonheme Fe enzymes that catalyze the oxidative cleavage of 1,4-dihydroxybenzene units. Reflecting the variety of HQDO substrates, the synthetic complexes feature both mono- and bidentate HQate ligands. The bidentate HQates cleanly provide five-coordinate, high-spin Fe(II) complexes with the general formula [Fe(Ph2Tp)(HLX)] (1X), where HLX is a HQate(1-) ligand substituted at the 2-position with a benzimidazolyl (1A), acetyl (1B and 1C), or methoxy (1D) group. In contrast, the monodentate ligand 2,6-dimethylhydroquinone (H2LF) exhibited a greater tendency to bridge between two Fe(II) centers, resulting in formation of [Fe2(Ph2Tp)2(μ-LF)(MeCN)]·[2F(MeCN)]. However, addition of one equivalent of “free” pyrazole (Ph2pz) ligand provided the mononuclear complex, [Fe(Ph2Tp)(HLF)(Ph2pz)]·[1F(Ph2pz)], which is stabilized by an intramolecular hydrogen bond between the HLF and Ph2pz donors. Complex 1F(Ph2pz) represents the first crystallographically-characterized example of a monoiron complex bound to an untethered HQate ligand. The geometric and electronic structures of the Fe/HQate complexes were further probed with spectroscopic (UV-vis absorption, 1H NMR) and electrochemical methods. Cyclic voltammograms of complexes in the 1X series revealed an Fe-based oxidation between 0 and −300 mV (vs. Fc+/0), in addition to irreversible oxidation(s) of the HQate ligand at higher potentials. The one-electron oxidized species (1Xoxox) were examined with UV-vis absorption and electron paramagnetic resonance (EPR) spectroscopies

An approach to randomization into surgical clinical trials

Recruitment of patients into surgical trials is difficult. One in five surgical RCTs is discontinued early and one in three trials remains unpublished1. This is particularly problematic when a study has a surgical and a non-surgical arm, and in the multimodal treatments that include surgery in many cancer trials. There is a recurring sticking point in randomizing patients because of the inherent difference between a preoperative surgical consultation and counselling patients about randomization. This could be resolved if it is accepted that there is no need for the patient to meet a surgeon until they have been assigned to a study arm involving surgery

Phase-field boundary conditions for the voxel finite cell method: surface-free stress analysis of CT-based bone structures

The voxel finite cell method employs unfitted finite element meshes and voxel quadrature rules to seamlessly transfer CT data into patient-specific bone discretizations. The method, however, still requires the explicit parametrization of boundary surfaces to impose traction and displacement boundary conditions, which constitutes a potential roadblock to automation. We explore a phase-field based formulation for imposing traction and displacement constraints in a diffuse sense. Its essential component is a diffuse geometry model generated from metastable phase-field solutions of the Allen-Cahn problem that assumes the imaging data as initial condition. Phase-field approximations of the boundary and its gradient are then employed to transfer all boundary terms in the variational formulation into volumetric terms. We show that in the context of the voxel finite cell method, diffuse boundary conditions achieve the same accuracy as boundary conditions defined over explicit sharp surfaces, if the inherent length scales, i.e., the interface width of the phase-field, the voxel spacing and the mesh size, are properly related. We demonstrate the flexibility of the new method by analyzing stresses in a human femur and a vertebral body

Gonadal hormones, but not sex, affect the acquisition and maintenance of a Go/No-Go odor discrimination task in mice

In mice, olfaction is crucial for identifying social odors (pheromones) that signal the presence of suitable mates. We used a custom-built olfactometer and a thirst-motivated olfactory discrimination Go/No-Go (GNG) task to ask whether discrimination of volatile odors is sexually dimorphic and modulated in mice by adult sex hormones. Males and females gonadectomized prior to training failed to learn even the initial phase of the task, which involved nose poking at a port in one location obtaining water at an adjacent port. Gonadally intact males and females readily learned to seek water when male urine (S+) was present but not when female urine (S−) was present; they also learned the task when non-social odorants (amyl acetate, S+; peppermint, S−) were used. When mice were gonadectomized after training the ability of both sexes to discriminate urinary as well as non-social odors was reduced; however, after receiving testosterone propionate (castrated males) or estradiol benzoate (ovariectomized females), task performance was restored to pre-gonadectomy levels. There were no overall sex differences in performance across gonadal conditions in tests with either set of odors; however, ovariectomized females performed more poorly than castrated males in tests with non-social odors. Our results show that circulating sex hormones enable mice of both sexes to learn a GNG task and that gonadectomy reduces, while hormone replacement restores, their ability to discriminate between odors irrespective of the saliency of the odors used. Thus, gonadal hormones were essential for both learning and maintenance of task performance across sex and odor type.We thank David Giese for help in programming the apparatus used in GNG testing and Alberto Cruz-Martin for comments on an early version of the manuscript. This work was supported by NIDCD grant DC008962 to JAC. (DC008962 - NIDCD grant)Accepted manuscrip

Analytic Approaches to the Evolution of Polarised Parton Distributions at Small xx

The $Q^2$ evolution of polarised parton distributions at small $x$ is studied. Various analytic approximations are critically discussed. We compare the full evolution with that obtained from the leading-pole approximation to the splitting functions, and show that the validity of this approximation depends critically on the $x \to 0$ behaviour of the starting distributions. A new analytic solution which is valid at small $x$ is obtained, and its domain of applicability is discussed.Comment: 14 pages, LATeX, 4 figures availabe as .uu-fil