Publications by authors named "James P Walsh"

A 73-year-old man with papillary thyroid cancer underwent total thyroidectomy and bilateral neck dissections. He was subsequently treated with 131I. The posttherapy scan showed radioiodine uptake at the left supraorbital region, which localized to a metallic surgical clip.

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Recent advances in high-pressure techniques offer chemists access to vast regions of uncharted synthetic phase space, expanding our experimental reach to pressures comparable to the core of the Earth. These newfound capabilities enable us to revisit simple binary systems in search of compounds that for decades have remained elusive. The most tantalizing of these targets are systems in which the two elements in question do not interact even as molten liquids-so-called immiscible systems.

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A new intermetallic compound, the first to be structurally identified in the Cu-Bi binary system, is reported. This compound is accessed by high-pressure reaction of the elements. Its detailed characterization, physical property measurements, and ab initio calculations are described.

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The crystal structure of the first oligomeric cobalt dioxolene complex, Co3(3,5-DBSQ)2((t)BuCOO)4(NEt3)2, 1, where DBSQ is 3,5-di-tert-butyl-semiquinonate, has been studied at various temperatures between 20 and 200 K. Despite cobalt-dioxolene complexes being generally known for their extensive ability to exhibit valence tautomerism (VT), we show here that the molecular geometry of compound 1 is essentially unchanged over the full temperature range, indicating the complete absence of electron transfer between ligand and metal. Magnetic susceptibility measurements clearly support the lack of VT between 8 and 300 K.

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A novel fluoride-centered triangular-bridged carboxylate complex, [Ni2Cr(μ3-F)(O2C(t)Bu)6(HO2C(t)Bu)3] (1), is reported. Simple postsynthetic substitution of the terminal pivalic acids in 1 with pyridine and 4-methylpyridine led to the isolation of [Ni2Cr(μ3-F)(O2C(t)Bu)6(C5H5N)3] (2) and [Ni2Cr(μ3-F)(O2C(t)Bu)6((4-CH3)C5H4N)3] (3). Structural and magnetic characterizations carried out on the series reveal a dominating antiferromagnetic interaction between the nickel and chromium centers leading to an S = (1)/2 ground state with a very unusual value of geff = 2.

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Structurally diverse mononuclear, dinuclear, and tetranuclear cobalt organophosphates and a three-dimensional framework based on a D4R cobalt phosphate are reported. The role of auxiliary ligands in determining the nuclearity of the phosphate clusters has further been established. Reaction of cobalt acetate tetrahydrate with 2,6-di-iso-propylphenylphosphate (dippH2) in methanol or DMSO in the presence of ancillary N-donor ligands leads to the formation of mononuclear octahedral cobalt phosphate [Co(dippH)2(py)4] (1), dinuclear octahedral cobalt phosphates [Co(dipp)(NN)(MeOH)2]2·2MeOH (NN = bpy 2; phen 3), tetrahedral cobalt phosphates [Co(dipp)(L)2]2·2(MeOH) (L = imz 4; dmpz 5) and symmetric and asymmetric tetranuclear tetrahedral cobalt phosphates [Co(dipp)(2-apy)]4 (6) and [Co4(dipp)4(2-apy)3(DMSO)]·(DMSO)·(H2O) (7), in nearly quantitative yields.

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Endogenous testosterone levels are inversely associated with cardiovascular risk in older men and men with cardiovascular disease. Current data on cardiovascular outcomes of testosterone therapy include only observational studies and adverse event monitoring in short-term trials that were not designed to measure cardiovascular outcomes. These studies have yielded conflicting results, and some have raised concerns that testosterone therapy may increase cardiovascular risk.

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The reaction of the hydrazone, 2-methoxy-6-(pyridin-2-yl-hydrazonomethyl) phenol (LH) with lanthanide(iii) nitrate salts in the presence of excess triethylamine afforded the heptanuclear Ln(iii) complexes: [Gd7(L)6(μ3-OH)8(NO3)4(H2O)]·(NO3)3·8CH3CN·H2O (), [Tb7(L)6(μ3-OH)8(NO3)4]·(NO3)3·9CH3CN·2CH3OH·3H2O (), [Dy7(L)6(μ3-OH)8(NO3)4(H2O)]·(NO3)3·7CH3CN·3H2O (), [Ho7(L)6(μ3-OH)8(NO3)4]·(NO3)3·11CH3CN·2CH3OH·2H2O () and [Er7(L)6(μ3-OH)8(NO3)4]·(NO3)3·8CH3CN·2CH3OH (). Single crystal X-ray diffraction studies reveal that these complexes are tri-cationic, possessing three nitrate counter anions. The heptanuclear ensemble is non-planar and consists of six [L](-) and eight μ3-OH ligands.

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Four novel mononuclear tetrahedral cobalt(II) complexes containing exocyclic mesoionic ligands of molecular formulae [Co(II)(L1)(X)2(MeCN)] X = Cl (1) or Br (2) and [Co(II)(L2)(X)2(MeCN)], X = Cl (3) or Br (4) have been reported. It is found that simple substitution of L1 (O donor in 1 and 2) by L2 (S donor in 3 and 4) results in switching of the single ion magnetic anisotropy parameter (D) from positive to negative, with a significant change in magnitude.

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The electron densities in two analogous dimetallic transition metal compounds, namely, [M2(μ-OH2)((t)BuCOO)4((t)BuCOOH)2(C5H5N)2] (M = Co(1), Ni(2)), were determined from combined X-ray and neutron single-crystal diffraction at 100 K. Excellent correspondence between the thermal parameters from X- and N-derived atomic displacement parameters is found, indicating high-quality X-ray data and a successful separation of thermal and electronic effects. Topological analysis of electron densities derived from high-resolution X-ray diffraction, as well as density functional theory calculations, shows no direct metal-metal bonding in either compound, while the total energy density at the bond critical points suggests stronger metal-oxygen interactions for the Ni system, in correspondence with its shorter bond distances.

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Mixed-metal uranium compounds are very attractive candidates in the design of single-molecule magnets (SMMs), but only one 3d-5f hetero-polymetallic SMM containing a uranium center is known. Herein, we report two trimeric heterodimetallic 3d-5f complexes self-assembled by cation-cation interactions between a uranyl(V) complex and a TPA-capped M(II)  complex (M=Mn (1), Cd (2); TPA=tris(2-pyridylmethyl)amine). The metal centers were strategically chosen to promote the formation of discrete molecules rather than extended chains.

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A series of water-bridged dinickel complexes of the general formula [Ni2(μ2-OH2)(μ2-O2C(t)Bu)2(O2C(t)Bu)2(L)(L')] (L = HO2C(t)Bu, L' = HO2C(t)Bu (1), pyridine (2), 3-methylpyridine (4); L = L' = pyridine (3), 3-methylpyridine (5)) has been synthesized and structurally characterized by X-ray crystallography. The magnetic properties have been probed by magnetometry and EPR spectroscopy, and detailed measurements show that the axial zero-field splitting, D, of the nickel(II) ions is on the same order as the isotropic exchange interaction, J, between the nickel sites. The isotropic exchange interaction can be related to the angle between the nickel centers and the bridging water molecule, while the magnitude of D can be related to the coordination sphere at the nickel sites.

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The reaction of 2-methoxy-6-(pyridin-2-ylhydrazonomethyl)phenol (LH) with Ln(III) (Ln = Gd, Tb, Dy, Ho) salts in the presence of an excess of triethylamine afforded [Gd4(L)4(μ4-OH)(μ3-OH)2(NO3)4]·(NO3)·4CH3CN·CH3OH·2H2O (1), [Tb4(L)4(μ4-OH)(μ3-OH)2(NO3)4]·(NO3)·4CH3CN·3H2O (2), [Dy4(L)4(μ4-OH)(μ3-OH)2(NO3)4]·(NO3)·6CH3CN·H2O (3), and [Ho4(L)4(μ4-OH)(μ-OH)2(NO3)4]·(NO3)·8CH3CN·3CH3OH·2H2O (4). All four complexes contain a monocationic tetranuclear core with a unique seesaw topology. The tetranuclear assembly is formed through the coordination of four [L](-), one μ4-OH, two μ3-OH, and four chelating nitrate ligands, with a charge-balancing nitrate counteranion.

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Objective: To report a rare case of diabetes caused by type B insulin resistance due to development of insulin receptor autoantibodies during treatment of hepatitis C with interferon-alpha and ribavirin.

Methods: Clinical and laboratory findings in the case are presented. The literature on type B insulin resistance and interferon-induced autoimmunity is reviewed.

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We have recently shown that elevated levels of free fatty acid (FFA) seen in insulin-resistant obese subjects are associated with endothelial dysfunction. L-carnitine, which is required for mitochondrial FFA transport/oxidation, has been reported to improve vascular function in subjects with diabetes and heart disease. Here, we tested the hypothesis that L-carnitine attenuates FFA-induced endothelial dysfunction.

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Diacylglycerol kinase (DGK) isoforms alpha and zeta were extracted from transfected cells that overexpressed these enzymes. We determined the lipid dependence of the binding of these isoforms to liposomes. The modulation by lipid of the rate of phosphorylation of diacylglycerol by these enzymes was also measured.

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Diacylglycerol kinases (DAGKs) catalyse ATP-dependent phosphorylation of sn-1,2-diacylglycerol that arises during stimulated phosphatidylinositol turnover. DAGKa is activated in vitro by Ca2+ and by acidic phospholipids. The regulatory region of DAGKa includes an N-terminal RVH motif and EF hands that mediate Ca2+-dependent activation.

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The present study was conducted among American undergraduates to examine the effects of public self-consciousness and repeated exposure to differing belief structures on individual belief structure change. This examination of both the individual and social origins of belief structure change complements the more typical investigations of how belief structures respond to the challenge of discrediting information. Individual differences multidimensional scaling analysis was employed to assess each subject's belief structure.

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