The first single-crystal X-ray structures of substituted vanadyl phthalocyanine materials reveal the high-valence vanadium ions (denoted as V(IV)), whose coordination by a highly electron-deficient ligand is facilitated by an axial oxo group. The metal center of the hydrophilic V═O core, encapsulated in F-rich hydrophobic pockets, reaches a coordination number of 6 by binding an additional H(2)O that, in turn, hydrogen-bonds with ketones, resulting in solvent-induced variable solid-state architectures. Fluoroalkyl (R(f)) ligand substituents hinder π-π stacking interactions and favor ordered long-range packing, as well as the facile formation of film materials that exhibit high thermal stability and oxidation resistance. Reversible redox chemistry and spectroscopic studies in both solution and the solid-state indicate single-site isolation in both phases and an R(f)-induced propensity for electron uptake and inhibition of electron loss. Repeated redox cycles reorganize the thin films to accommodate Li(+) ions and facilitate their migration. The facile reduction, combined with high stability and ease of sublimation imparted by the R(f) scaffold that suppresses oxidations, recommends the new materials for sensors, color displays, electronic materials, and redox catalysts, as well as other applications.
Anencephaly results from defects in neural tube closure early in gestation and, to the authors' knowledge, has not been reported in dogs. In this case, the canine fetus was stillborn at the 62nd day of gestation and had a hypoplastic calvarium, with flattened base of the skull and shallow orbits, causing protrusion of the eyes. Macroscopically, the brain was completely missing. Histologically, well-differentiated nerve fibers, fragments of cerebellar folia, and ganglia with large neurons and glial cells were detected in a loose stroma in sections through the cranial bone and adjacent soft tissue in the rudimentary cranial cavity. Immunohistochemically, single cells within the stroma expressed NeuN, consistent with mature neurons, whereas intracranial ganglion cells and nerves had mild expression of doublecortin. The presence of many immature, and only a few mature, neurons in the rudimentary nerve tissue in this case indicates a failure of physiological brain development and differentiation.
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