Polyoxovanadium(IV) sulfite compounds: Synthesis, structural, and physical studies

An unexplored family of polyoxometalates has evolved through the synthesis and structural characterization of vanadium(IV) sulfite heteropolyanions. The hexanuclear vanadium(IV) compound, which is ferromagnetic down to 2 K, exhibits a unique structural motif for such metal species, with a central cubic {M<sub>4</sub>O<sub>2</sub>(OH)<sub>2</sub>} fragment and metal centers at two of the corners of the cluster

Surgical thoracic sympathectomy induces structural and biomechanical remodeling of the thoracic aorta in a porcine model

Background: Sympathetic innervation exerts marked effects on vascular smooth muscle cells, including a short-term homeostatic (vasoconstrictor) and a direct trophic action promoting differentiation. However, the role of sympathetic nervous system in long-term structural and functional modulation of the aortic wall is yet undefined. Methods: Six Landrace pigs underwent bilateral thoracic sympathectomy from the stellate to T8 ganglion, whereas 10 pigs underwent sham operation. Animals were sacrificed 3 mo postoperatively. Histometrical examination was performed on specimens from the thoracic (TA) and abdominal aorta (AA) utilizing an image-processing system. A uniaxial tensile tester was utilized for biomechanical evaluation; parameters of extensibility, strength, and stiffness of aortic tissue were calculated. Results: Structural aortic remodeling of sympathectomized animals was observed, including increased inner aortic diameter in TA (15.3 ± 0.4 versus 10.4 ± 0.2 mm, P < 0.001) and AA (6.7 ± 0.3 versus 5.3 ± 0.2 mm, P = 0.002), and increased wall thickness in TA (2.0 ± 0.1 versus 1.6 ± 0.1 mm, P < 0.001) but not AA. Microscopic image analysis revealed increased elastin (TA: 50.1 ± 1.1 versus 29.7% ± 0.6%, P < 0.001; AA: 20.4 ± 2.1 versus 16.3% ± 0.6%, P = 0.03) and collagen density (only in TA: 22.0 ± 0.9 versus 15.4% ± 0.5%, P < 0.001), and decreased smooth muscle density (TA: 27.6 ± 1.3 versus 54.9% ± 0.7%, P < 0.001; AA: 57.2 ± 1.5 versus 63.4% ± 0.8%, P < 0.001). Sophisticated biomechanical analysis demonstrated that following sympathectomy, TA was equally extensible but manifested augmented strength (1344 ± 73 versus 1071 ± 52 kPa, P = 0.004) and stiffness (6738 ± 478 versus 5026 ± 273 kPa, P = 0.003), in accordance with extracellular matrix protein accumulation in that region. Differences in the AA were non-significant. Conclusions: Chronic thoracic sympathetic denervation causes significant structural and biomechanical remodeling of the thoracic aorta. Possible clinical implications for patients undergoing thoracic sympathectomy or chronically treated with sympathetic blockers require further investigation. © 2012 Elsevier Inc. All rights reserved

Oxovanadium(IV)-sulfite compounds: Synthesis and structural and physical studies

Reaction of VIVOCl2 in strongly acidic aqueous solution with either (NH4)(2)SO3 or Na2SO3 and Bu4NBr at similar to 70 degrees C in the pH range 2.5-4.5 gives the clusters (NH4)(2){V-4(IV)(mu(4)-O)(2)(mu(3)-OH)(2)]((VO)-O-IV)(2)(mu(3)-SO3)( 4)O-4(H2O)(2)} and (n-Bu4N)(2){V-4(IV)(mu(4)-O)(2)(mu(3)-OH)(2)]((VO)-O-IV)(2)(mu(3)-SO 3)(4)O-4(H2O)(2)}, respectively. Reaction of (NH4VO3)-O-V with (NH4)(2)SO3 resulted in the isolation of the first compound. When the latter reaction is carried out in the presence of MgO, compound (NH4)(VO)-O-IV(SO3)(1.5)H2O](infinity)center dot 2.5H(2)O was isolated instead. Compound (n-Bu4N)(2){V-4(IV)(mu(4)-O)(2)(mu(3)-OH)(2)]((VO)-O-IV)(2)(mu(3)-SO 3)(4)O-4(H2O)(2)} and (NH4)(VO)-O-IV(SO3)(1.5)H2O](infinity)center dot 2.5H(2)O were characterized by X-ray structure analysis. The crystal structure of species (n-Bu4N)(2){IV4IV(mu(4)-O)(2)(mu(3)-OH)(2)]((VO)-O-IV)(2)(mu(3)-SO3)(4) O-4(H2O)(2)} revealed a unprecedented hexanuclear cluster consisting of a cubane core M-4(mu(4)-O)(2)(mu(3)- OH)(2)] connected to two other metal atoms through the core oxo-groups and four mu(3)-SO3 bridges. Compound (NH4)VIVO(SO3)(1.5)H2O](infinity)center dot 2.5H(2)O represents a rare example of an open-framework species prepared under mild conditions. Cyclic voltammetric examination of compound (n-Bu4N)(2){IV4IV(mu(4)-O)(2)(mu(3)-OH)(2)]((VO)-O-IV)(2)(mu(3)-SO3) (4)O-4(H2O)(2)] revealed a redox process which was assigned to the oxidation of one core of vanadium(IV) to vanadium(V)