Analysis of chromates for traces of Cr(III) by solvent extraction and inductively coupled plasma atomic emission spectrometry

Summary A method for the determination of quantities of 0.5–500 g of Cr(III) in the presence of chromates and dichromates is described. The samples are dissolved in an aqueous solution buffered at pH 7.0; the Cr(III) is selectively chelated with 2-thenoyltrifluoroacetone and extracted into xylene. The extracted chromium is analyzed using inductively coupled plasma emission spectrometry. Extraction of 1.0 g Cr(III) from 5.0 mg K₂Cr₂O₇ was accomplished and easily determined in a volume of 25 ml of xylene. The relative standard deviation for the determination of Cr(III) contents ranging from 4.0 × 10^–8 g/ml to 2.0 × 10^–8 g/ml was ± 0.079. Using a minimum signal to noise ratio of 101, the detection limits of the method were determined to be approximately 2.0 × 10^–8 g/ml xylene. Chloride, high surface area silica, and easily oxidized amorphous boron give rise to only minor interferences.

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Analyse von Cr(III)-Spuren in Chromaten durch Extraktion und ICP-Atomemissionsspektrometrie

Zusammenfassung Ein Verfahren wird beschrieben zur Bestimmung von 0,5–500 g Cr(III) in Gegenwart von Chromaten und Dichromaten. Die Proben werden in Pufferlösung pH 7,0 gelöst, und 2-Thenoyltrifluoraceton behandelt und Cr(III) selektiv mit Xylol extrahiert. Die Bestimmung erfolgt durch ICP-Spektrometrie. 1,0 g Cr(III) konnte von 5,0 mg K₂Cr₂O₇ getrennt und in einen Volumen von 25 ml Xylol bestimmt werden. Die relative Standardabweichung im Bereich von 4,0 · 10^–8 bis 2,0 · 10^–7 g Cr(III)/ml betrug ± 0,079. Bei einem Verhältnis SignalUntergrund = 101 wurden Nachweisgrenzen um 2,0 · 10^–8 g/ml gefunden. Störungen durch Chlorid, Siliciumdioxid und amorphes Bor sind gering.

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This work was supported by the U.S. Department of Energy (DOE) under contract number DE-AC04-76-DP00789

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A U.S. DOE facility     

A non-MRA C^r Frame Wavelet with Rapid Decay

A generalized filter construction is used to build an example of a non-MRA normalized tight frame wavelet for dilation by 2 in . This example has the same multiplicity function as the Journé wavelet, yet has a Fourier transform and can be made to be for any fixed postive integer . L. Baggett and P. Jorgensen were supported by a US–NSF Focused Research Group (FRG) grant.     

Limit points badly approximable by horoballs

For a proper, geodesic, Gromov hyperbolic metric space X, a discrete subgroup of isometries Γ whose limit set is uniformly perfect, and a disjoint collection of horoballs {H _j }, we show that the set of limit points badly approximable by {H _j } is absolutely winning in the limit set Λ(Γ). As an application, we deduce that for a geometrically finite Kleinian group acting on ${\mathbb{H}^{n+1}}$ , the limit points badly approximable by parabolics, denoted BA(Γ), is absolutely winning, generalizing previous results of Dani and McMullen. As a consequence of winning, we show that BA(Γ) has dimension equal to the critical exponent of the group. Since BA(Γ) can alternatively be described as the limit points representing bounded geodesics in the quotient ${\mathbb{H}^{n+1}/\Gamma}$ , we recapture a result originally due to Bishop and Jones.     

Direct observation of the phenomenology of a solid thermal explosion using time-resolved proton radiography

We present a new phenomenology for burn propagation inside a thermal explosion based on dynamic radiography. Radiographic images were obtained of an aluminum cased solid cylindrical sample of a plastic bonded formulation of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine. The phenomenology observed is ignition followed by cracking in the solid accompanied by the propagation of a radially symmetric front of increasing proton transmission. This is followed by a further increase in transmission through the sample, ending after approximately 100 micros. We show that these processes are consistent with the propagation of a convective burn front followed by consumption of the remaining solid by conductive particle burning.     

Genetic microheterogeneity of human transthyretin detected by IEF

Mutations of the human transthyretin (TTR) gene have attracted medical interest as a cause of amyloidosis. Recently, we have described in detail an electrophoretic procedure with PAGE followed by IEF in urea gradients for the study of the microheterogeneity of TTR monomers (Altland, K., Winter, P., Sauerborn, M. K., Electrophoresis 1999, 20, 1349-1364). In this paper, we present a study on 49 different mutations of TTR including 33 that result in electrically neutral amino acid substitutions. The aims of the investigation were to test the sensitivity of the procedure to detect TTR variants in patients with TTR amyloidosis and their relatives and to identify some common characteristics that could explain the amyloidogenicity of these variants. We found that all tested amyloidogenic mutations could be detected by our method with the exception of those for which the corresponding variant was absent in plasma samples. Most of the electrically neutral amyloidogenic TTR variants had in common a reduced conformational stability of monomers by the activity of protons and urea. For three variants, e.g. TTR-F64L, TTR-I107V and TTR-V122I, the monomers had a conformational stability close to that of normal monomers but we found experimental and structural arguments for a weakening of the monomer-monomer contact. All types of amyloidogenic mutations affected the stability of TTR tetramers.     

Ring current effects in crystals. Evidence from 13C chemical shift tensors for intermolecular shielding in 4,7-di-t-butylacenaphthene versus 4,7-di-t-butylacenaphthylene

13C chemical shift tensor data from 2D FIREMAT spectra are reported for 4,7-di-t-butylacenaphthene and 4,7-di-t-butylacenaphthylene. In addition, calculations of the chemical shielding tensors were completed at the B3LYP/6-311G** level of theory. While the experimental tensor data on 4,7-di-t-butylacenaphthylene are in agreement with theory and with previous data on polycyclic aromatic hydrocarbons, the experimental and theoretical data on 4,7-di-t-butylacenaphthene lack agreement. Instead, larger than usual differences are observed between the experimental chemical shift components and the chemical shielding tensor components calculated on a single molecule of 4,7-di-t-butylacenaphthene, with a root mean square (rms) error of +/-7.0 ppm. The greatest deviation is concentrated in the component perpendicular to the aromatic plane, with the largest value being a 23 ppm difference between experiment and theory for the 13CH2 carbon delta11 component. These differences are attributed to an intermolecular chemical shift that arises from the graphitelike, stacked arrangement of molecules found in the crystal structure of 4,7-di-t-butylacenaphthene. This conclusion is supported by a calculation on a trimer of molecules, which improves the agreement between experiment and theory for this component by 14 ppm and reduces the overall rms error between experiment and theory to 4.0 ppm. This intermolecular effect may be modeled with the use of nuclei independent chemical shieldings (NICS) calculations and is also observed in the isotropic 1H chemical shift of the CH2 protons as a 4.2 ppm difference between the solution value and the solid-state chemical shift measured via a 13C-1H heteronuclear correlation experiment.     

Synthesis, structural, and magnetic characterization of linear and bent geometry cobalt(II) and nickel(II) amido complexes: evidence of very large spin-orbit coupling effects in rigorously linear coordinated Co2+

The complexes M(II){N(H)Ar(Pr(i)(6))}(2) (M = Co, 1 or Ni, 2; Ar(Pr(i)(6)) = C(6)H(3)-2,6(C(6)H(2)-2,4,6-Pr(i)(3))(2)), which have rigorously linear, N-M-N = 180°, metal coordination, and M(II){N(H)Ar(Me(6))}(2) (M = Co, 3 or Ni, 4; Ar(Me(6)) = C(6)H(3)-2,6(C(6)H(2)-2,4,6-Me(3))(2)), which have bent, N-Co-N = 144.1(4)°, and N-Ni-N = 154.60(14)°, metal coordination, were synthesized and characterized to study the effects of the metal coordination geometries on their magnetic properties. The magnetometry studies show that the linear cobalt(II) species 1 has a very high ambient temperature moment of about 6.2 μ(B) (cf. spin only value = 3.87 μ(B)) whereas the bent cobalt species 3 had a lower μ(B) value of about 4.7 μ(B). In contrast, both the linear and the bent nickel complexes 2 and 4 have magnetic moments near 3.0 μ(B) at ambient temperatures, which is close to the spin only value of 2.83 μ(B). The studies suggest that in the linear cobalt species 1 there is a very strong enhanced spin orbital coupling which leads to magnetic moments that broach the free ion value of 6.63 μ(B) probably as a result of the relatively weak ligand field and its rigorously linear coordination. For the linear nickel species 2, however, the expected strong first order orbital angular momentum contribution does not occur (cf. free ion value 5.6 μ(B)) possibly because of π bonding effects involving the nitrogen p orbitals and the d(xz) and d(yz) orbitals (whose degeneracy is lifted in the C(2h) local symmetry of the Ni{N(H)C(ipso)}(2) array) which quench the orbital angular momentum.