Carbaporphyrinoid chemistry has a silver lining! silver(III) oxybenzi-, oxynaphthi-, tropi-, and benzocarbaporphyrins

[structure: see text] Carbaporphyrinoid systems with semiquinone, cycloheptatriene, or indene subunits react under mild conditions with silver(I) acetate to give stable silver(III) organometallic derivatives.     

Structural and magnetoelectric properties of MFe<Subscript>2</Subscript>O<Subscript>4</Subscript>–PZT (M = Ni,Co) and La<Subscript>x</Subscript>(Ca,Sr)<Subscript>1-x</Subscript>MnO<Subscript>3</Subscript>–PZT multilayer composites

Thick-film layered magnetoelectric composites consisting of ferromagnetic and ferroelectric phases have been synthesized with nickel ferrite (NFO), cobalt ferrite, La_0.7Sr_0.3MnO₃ (LSMO), or La_0.7Ca_0.3MnO₃ (LCMO) and lead zirconate titanate (PZT). Structural, magnetic, and ferromagnetic resonance characterization shows evidence for defect-free ferrites, but deterioration of manganite parameters. The resistivity and dielectric constants are smaller than expected values. The magnetoelectric effect (ME) is stronger in ferrite–PZT than in manganite–PZT. The ME voltage coefficient _E at room temperature is the highest in NFO–PZT and the smallest for LCMO–PZT. The transverse ME effect is an order of magnitude stronger than the longitudinal effect. The magnitude of _E correlates well with magnetic permeability for the ferrites. PACS 75.80.+q; 75.70.Gg; 75.60.-d     

Preparation of a novel diphosphine-palladium macrocyclic complex possessing a molecular recognition site. Oxidative addition studies

A disphosphine-palladium(0) complex capable of recognising barbiturates has been prepared. Oxidative addition studies with a barbitiurate:aryl iodide conjugate provided new Pd(ii) complexes where the positioning of the Pd-bound aryl group is controlled by the molecular recognition event.     

Improved convergence in block copolymer self-consistent field theory by Anderson mixing

A modification to real space polymeric self-consistent field theory algorithms that greatly improves the convergence properties is presented. The method is based on Anderson mixing [D. G. Anderson, J. Assoc. Comput. Mach. 12, 547 (1965)], and each iteration computed takes negligibly longer to perform than with other methods, but the number of iterations required to reach a high accuracy solution is greatly reduced. No a priori knowledge of possible phases is required to apply this method. We apply our approach to a standard diblock copolymer melt, and demonstrate iteration reductions of more than a factor of 5 in some cases.     

Nitrogen isotope analysis of ammonium in aqueous solutions using a perfluorosulfonated ionomer membrane for solid-phase microextraction

The use of custom-made solid-phase microextraction (SPME) fibers coated with a perfluorosulfonated ionomer, Nafion, was investigated for nitrogen isotopic analysis of ammonium in aqueous solutions. Aqueous ammonium was converted to ammonia by addition of a base, followed by absorption from the headspace, desorption in the injection port of a gas chromatograph, and analysis by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). Fibers coated with a Nafion tubing were chosen due to a higher fiber-gas distribution constant and a higher Nafion thickness than fibers coated with Nafion solution, both leading to a higher amount of ammonia absorbed at equilibrium. The Nafion membrane-coated fiber absorbed approximately 20 times more than a commercial polydimethylsiloxane (PDMS) fiber. The isotopic fractionation between fiber and gas was 1.0117 +/- 0.0009 (standard deviation, SD, of all measurements) at an initial ammonia gas concentration of 21-210 microM. At 390 microM initial gas concentration it was slightly lower. When sampling from liquid samples, an ammonium concentration of 10 mM was needed to obtain a sufficient amount of ammonia absorbed. Modeling of the absorption at different temperatures showed that the absorption was approximately constant in the temperature range suitable for SPME experiments. Absorption at room temperature was therefore used for simplicity. A pilot study was conducted in which absorption was achieved from a single 9 microL droplet of sample. The preliminary results showed that delta(15)N analysis was possible for only 0.4-0.5 micromol of ammonium with a SD of 0.8 per thousand (n = 5).     

Studies on the conformation of α-arylcinnamic acids and their esters: Crystal structures of methyl (E)-2,3-bis(3,4-dimethoxyphenyl)propenoate and methyl (Z)-2,3-bis(3,4-dimethoxyphenyl)propenoate

The conformations of stereoisomers of -arylcinnamic acids and their esters are discussed based on crystal structures of the E and Z forms of 2,3-bis(3,4-dimethoxyphenyl)propenoic acid and its methyl ester. In the E forms of the cinnamic acid and the cinnamic acid ester, the plane of the -aryl substituent is approximately perpendicular to that of the rest of the molecule. In the Z forms the plane of the carboxyl or methoxycarbonyl group is approximately perpendicular to that of the ethylenic group, and both the aromatic group planes are significantly twisted out of the ethylenic group plane. Crystal structures of methyl (E)-2,3-bis(3,4-dimethoxyphenyl)propenoate (space group P2₁/n with a = 8.1697(5), b = 11.3882(9), c = 19.7766(9) Å, = 90.058(4)°, V = 1840.0(2) ų, and Z = 4), monoclinic methyl (Z)-2,3-bis(3,4-dimethoxyphenyl)propenoate (space group P2₁/n with a = 11.183(2), b = 5.640(2), c = 29.737(7) Å, = 99.19(2)°, V = 1851.4(9) ų, and Z = 4), and orthorhombic methyl (Z)-2,3-bis(3,4-dimethoxyphenyl)propenoate (space group P2₁2₁2₁ with a = 8.849(4), b = 24.288(9), c = 8.734(3) Å, V = 1877(1) ų, and Z = 4) are reported.     

The Coloring Ideal and Coloring Complex of a Graph

Let G be a simple graph on d vertices. We define a monomial ideal K in the Stanley-Reisner ring A of the order complex of the Boolean algebra on d atoms. The monomials in K are in one-to-one correspondence with the proper colorings of G. In particular, the Hilbert polynomial of K equals the chromatic polynomial of G.The ideal K is generated by square-free monomials, so A/K is the Stanley-Reisner ring of a simplicial complex C. The h-vector of C is a certain transformation of the tail T(n) = n ^d – (n) of the chromatic polynomial of G. The combinatorial structure of the complex C is described explicitly and it is shown that the Euler characteristic of C equals the number of acyclic orientations of G.     

Shifted identical bands: A new phenomenon

The levels in ¹⁶²Gd were identified in spontaneous fission studies. Its transition energies are remarkably similar to those in ¹⁶⁰Gd. From that work, an analysis of yrast bands in even-even proton to neutron-rich Ba to Pb nuclei led to the discovery of a new phenomenon, shifted identical bands (SIB). SIBs are yrast bands in neighboring nuclei (a, b) with moments of inertia which are identical when shifted by a constant amount κ, so J _1a (1+κ)=J _1b , from 2⁺ to 8⁺ and higher to 16⁺. Out of over 700 comparisons, 55 SIBs were found from stable to the most neutron-rich Ce-W nuclei with $\left| {\bar k} \right|$ between 1.5% and 13%, where the spread in κ is less than ±1%, and only four identical bands ( $\bar k \cong 0$ ). As examples, we found for ¹⁵⁸Sm-¹⁶⁰Gd, $\bar k = \left( { - 3.2_{ - 0.2}^{ + 0.1} } \right)\%$ (where the ± is the total spread in κ from ?3.1 to ?3.4); ¹⁵⁶Nd-¹⁶⁰Gd, (?10.6 _?0.2 ^+0.4 )%; ¹⁵⁸Sm-¹⁶⁰Sm, (3.4 _?0.3 ^+0.5 )%. The J ₁ values were fitted to a variable moment of inertia model with parameters J ₀ and C whose values correlate with the SIB J ₁ values. The SIBs are not correlated either with deformation or with the N _p N _n product of the IBA model.     

Visualization of flameholding mechanisms in a supersonic combustor using PLIF

Laser-induced fluorescence of OH and CH₂O was imaged to investigate the flame stabilization mechanism in a flameholder with a Mach 2.4 free stream. Ethylene was burned in a rectangular cavity with two points of injection: the aft wall and the cavity floor. When injected from the aft wall, the fuel came into immediate contact with hot combustion products from the reaction zone under the shear layer. Primary combustion occurred under the shear layer and in the aft region of the cavity volume. In contrast, when fuel was injected from the floor, a jet-driven recirculation zone of hot products near the upstream wall of the cavity served as a flameholder. The reaction then occurred on the underside of the shear layer. In conditions near lean blowout, significant changes in the flameholding mechanisms were observed. Improved CH₂O fluorescence signal was obtained by taking advantage of the long fluorescence lifetime at low pressures and delaying the camera gate to reduce the background signal.