Algebraic study of chiral anomalies

The algebraic structure of chiral anomalies is made globally valid on non-trivial bundles by the introduction of a fixed background connection. Some of the techniques used in the study of the anomaly are improved or generalized, including a systematic way of generating towers of descent equations.This work was supported in part by the Director, Office of Energy Research, Office of High Energy and Nuclear Physics, Division of High Energy Physics of the U.S. Department of Energy under contract DE-AC03-76SF00098 and in part by the National Science Foundation under research grant PHY81-18547     

Structure and dynamics of ND3BF3 in the solid and gas phases: a combined NMR,neutron diffraction,and Ab initio study

The decrease in D-->A bond lengths, previously reported for some Lewis acid/base complexes, in going from the gas to the solid phases is investigated by obtaining an accurate crystal structure of solid ND(3)BF(3) by powder neutron diffraction. The B-N internuclear distance is 1.554(3) A, 0.118 A shorter than the most recent gas-phase microwave value and 0.121 A shorter than the single molecule geometry optimized (1.672 A, CISD/6-311++G(d,p)) bond length. The crystal structure also shows N-D.F-B hydrogen bonds. The effects of this change in structure and of intermolecular hydrogen-bonding on nuclear magnetic shielding (i.e., chemical shifts) and the nuclear quadrupolar coupling constants (QCC) are investigated by ab initio molecular orbital and density functional theory calculations. These calculations show that the nitrogen ((15)N and (14)N) and boron ((11)B and (10)B) chemical shifts should be rather insensitive to changes in r(BN) and that the concomitant changes in molecular structure. Calculations on hydrogen-bonded clusters, based on the crystal structure, indicate that H-bonding should also have very little effect on the chemical shifts. On the other hand, the (11)B and (14)N QCCs show large changes because of both effects. An analysis of the (10)B[(19)F] line shape in solid ND(3)(10)BF(3) yields a (11)B QCC of +/-0.130 MHz. This is reasonably close an earlier value of +/-0.080 MHz and the value of +/-0.050 MHz calculated for a [NH(3)BF(3)](4) cluster. The gas-phase value is 1.20 MHz. Temperature-dependent deuterium T(1) measurements yield an activation energy for rotation of the ND(3) group in solid ND(3)BF(3) of 9.5 +/- 0.1 kJ/mol. Simulations of the temperature-dependent T(1) anisotropy gave an E(a) of 9.5 +/- 0.2 kJ/mol and a preexponential factor, A, of 3.0 +/- 0.1 x 10(12) s(-)(1). Our calculated value for a [NH(3)BF(3)](4) cluster is 16.4 kJ/mol. Both are much higher than the previous value of 3.9 kJ/mol, from solid-state proton T(1) measurements.     

Gas Phase Catalysis by Metal Nanoparticles in Nanoporous Alumina Membranes

Nanoporous alumina membranes, loaded with palladium and ruthenium nanoparticles of various size, were used for gas phase hydrogenation of 1, 3‐butadiene and for oxidation of carbon monoxide, respectively. Those membranes contain 10⁹ ‐ 10¹¹ pores per cm², all running perpendicular to the surface. Membrane discs of 20 mm in diameter and only 60 μm thick, incorporated in a reactor in which the reactants can be pumped in a closed circuit through the pores, turned out to very actively catalyze hydrogenation of butadiene (Pd) and oxidation of CO (Ru). The activity of the Pd catalysts depends characteristically on the particles size, the gas flow, and of the educts ratio. As could be expected, larger particles are less active than smaller ones, whereas increasing gas flows in case of hydrogenation accelerates the reactions. Excessive hydrogen reduces selectivity with respect to the various butenes, but favours formation of butane.     

New designs for inhibitors of the NF-κB: DNA binding

We present a series of new inhibitors of the association between nuclear factor kappa B (NF-B) and the corresponding B site in DNA. They were designed using the lead compound 15-deoxy-^12,14 -prostaglandin J₂ (PGJ2), which is a natural product with demonstrated inhibitory efficiency for this system. First, the binding mode of PGJ2 to NF-B was unraveled by GOLD docking calculation. Subsequently, substitutions were made to PGJ2 to optimize its association with NF-B. Care was taken not to strongly increase the reactivity of the new compounds, and to keep the overall shape, size and hydrophilicity of the lead compound, which should render them a similar bioavailability. Molecular mechanics calculations were performed to decide on the suitability of the substitutions, and to evaluate the energies of association with NF-B. Density functional theory calculations were performed also to study the overall reactivity of the substituted drugs towards NF-B. Important general conclusions were obtained, concerning the improvement of these natural inhibitors; namely, a set of rational methodologies were deduced to improve the association between the PGJ2 derivatives and NF-B, and their efficiency demonstrated by generating a set of substituted complexes, some of them with a very much increased affinity for NF-B, opening new doors to enlarge the therapeutic capabilities of this class of drugs.     

13C-nmr of carbonyl compounds 1. Stereodynamic behaviour of acyclic and cyclic dienones

The conformational mobility of a series of conjugated dienones is investigated by low-temperature NMR- and IR-spectroscopy and interpreted in terms of substituent effects.     

(η3‐Allyl‐2κ3C)(chloro‐1κCl)(μ‐N,N′‐diethyldithioxamidato‐1:2κ4S,S′:N,N′)[diphenyl(2‐pyridyl)phosphine‐1κP]palladium(II)platinum(II) chloroform solvate

The title compound, [PdPtCl(C₃H₅)(C₆H₁₀N₂S₂)(C₁₇H₁₄NP)]·CHCl₃, was obtained by deprotonation of the initial platinum(II) complex of the di­thio­xamide and subsequent reaction with [Pd(η³‐C₃H₅)(μ‐Cl)]₂. Both metal atoms exhibit a square‐planar coordination geometry, with the two planes forming a dihedral angle of 21.7 (2)°. The di­thio­xamide bis‐chelating bridge is flat.     

New approach to calibrating conductivity meters in the low conductivity range

There is currently a major issue with the calibration of conductivity meters used for high purity water: the lack of availability of a reference material or reference methods for low conductivity ranges (conductivity below 1 S cm^–1 at 25.0 °C, resistivity >1 M cm at 25.0 °C). This paper describes the current status of conductivity measurements in high purity water. A new and improved approach, currently being investigated, should allow us to make the calibration of conductivity meters used for low conductivity ranges traceable to the SI.Milipore, Milli-Q and Elix are registered trademarks of Millipore Corporation.     

On the mechanism of nanopore filling of SAPO-5 molecular sieve by nitrogen molecules

SAPO-5 molecular sieve was synthesized according to patent literature and characterized with X-ray diffraction, electron microscopy (SEM, TEM), and solid state magic angle spinning NMR spectroscopy. The material of particles in the micrometer region was found to consist of ca. 20 nm microcrystallites packed in mostly parallel orientation to ca. 200 nm sized agglomerates. The nitrogen adsorption isotherm was measured at 77.6 K over ca. 7 decades of pressure up to pore saturation. The course of the isotherm is interpreted to consist of filling of the nanopores (diameter, 0.73 nm) up to 2N(2)/unit cell, subsequent multilayer adsorption on the outer surface of the agglomerates, and, finally, pore condensation in the interparticle adsorption space. The nanopore adsorption can be quantitatively reproduced with the statistical mechanical model of a quasi one-dimensional lattice gas taking intermolecular interactions into account. The evaluated energy parameters are of physically reasonable magnitude and agree with literature data. The multilayer part of the adsorption isotherm can be well represented by the Brunauer-Emmett-Teller model yielding a specific outer space area (63 m(2) g(-)(1)) which is consistent with estimated geometrical and pore size analysis data.     

5-isobutyl-3-methyl-2-furancarbaldehyde,a new monoterpenoid from the essential oil of tagetes glandulifera schrank

The new monoterpenoid 5-isobutyl-3-methyl-2-furancarbaldehyde was isolated from Tagetes glandulifera Schrank and its structure confirmed by synthesis.