The Oxidation of Heterogeneous Tl/Ni/P‐Alloys — Preparation and Crystal Structures of the Thallium Nickel Phosphates TlNi4(PO4)3, Tl4Ni7(PO4)6, and Tl2Ni4(P2O7)(PO4)2

Single crystals of the first anhydrous thallium nickel phosphates were prepared by reaction of heterogeneous Tl/Ni/P alloys with oxygen. TlNi₄(PO₄)₃ (pale‐yellow, orthorhombic, space group Cmc2₁, a = 6.441(2)Å, b = 16.410(4)Å, c = 9.624(2)Å, Z = 4) crystallizes with a structure closely related to that of NaNi₄(PO₄)₃. Tl₄Ni₇(PO₄)₆ (yellow‐brown, monoclinic, space group Cm, a = 10.711(1)Å, b = 14.275(2)Å, c = 6.688(2)Å, β = 103.50(2)°, Z = 8) is isotypic with Na₄Ni₇(PO₄)₆, and Tl₂Ni₄(P₂O₇)(PO₄)₂ (brown, monoclinic, space group C2/c, a = 10.389(2)Å, b = 13.888(16)Å, c = 18.198(3)Å, β = 103.1(2)°, Z = 8) adopts the K₂Ni₄(P₂O₇)(PO₄)₂ structure. Tl₂Ni₄(P₂O₇)(PO₄)₂ could also be prepared in nearly single phase form by reaction of Tl₂CO₃, NiO, and (NH₄)₂HPO₄.     

Half-life of41Ca

The half-life of⁴¹Ca has been redetermined to be (1.01 ±0.10)×10⁵ yr from the specific activity of a sample of enriched calcium material and its⁴¹Ca concentration. The activity was measured with a Si(Li) detector via the 3.3-keV X rays emitted in the electron capture decay of⁴¹Ca to⁴¹K. The⁴¹Ca concentration was measured by mass spectrometry. Since our result agrees well with the two most recent half-life measurements of Mabuchi et al. (1974), (1.13±0.12)×10⁵ yr, and Klein et al. (1990), (1.03±0.07)×10⁵ yr, we recommend the weighted mean of these three measurements, t_1/2=(1.04±0.05)×10⁵ yr, as the most accurate value of the half-life of⁴¹Ca.Dedicated to Prof. Dr. P. Kienle on the occasion of his 60th birthday     

Chemical Constituents of Brown Rice Grain (<Emphasis Type="Italic">Oryza sativa</Emphasis>)

One new compound 3,7,11,15,19-pentamethyl-9α,10α,11α,17α,18α-pentahydroxy-n-tetracosan-1-oxy-p-hydroxycaffeoate (oryzaterpenyl caffeoate) (1), together with three known fatty acids linoleic acid, stearic acid and myristic acid were isolated and identified from the rice grain of Oryza sativa. The structure of the new compound was elucidated by 1D and 2D NMR spectroscopic techniques (¹H-¹HCOSY, ¹H-¹³C HETCOR) aided by EI-MS, and IR spectra. __________ Published in Khimiya Prirodnykh Soedinenii, No. 6, pp. 535–537, November–December, 2005.     

Measurement of lead-210, bismuth-210, and polonium-210 in environmental samples

Mathematical equations governing the ratio of²¹⁰Bi/²¹⁰Pb and²¹⁰Po/²¹⁰Pb activities are used to explain the ingrowth of²¹⁰Bi and²¹⁰Po in environmental samples during post collection. Procedures are described for radiochemical separation of²¹⁰Pb,²¹⁰Bi, and²¹⁰Po in a state of radioactive disequilibrium and quantification by alpha- and beta-counting. Also, the special case is considered where²¹⁰Bi is in equilibrium with²¹⁰Pb, but both are in disequilibrium with²¹⁰Po. In this case, the activities of both²¹⁰Pb and²¹⁰Po are computed by measuring²¹⁰Po activity twice, using alpha-counting.     

Synthesis and biological evaluation of 5-substituted-4-nitroimidazole ribonucleosides

The imidazole nucleosides, 4(5)-bromo-5(4)-nitro-1-β-D-ribofuranosylimidazoles, have been prepared via glycosylation of the trimethylsilylated aglycone, 4(5)-bromo-5(4)-nitroimidazole, with tetra-O-acetyl-β-D-ribo-furanose followed by removal of the acetyl protecting groups. The 5-bromo-4-nitro-1-β-D-ribofuranosylimidazole nucleoside was acetonated to produce 5-bromo-4-nitro-1-(2,3-O-isopropylidene-β-D-ribofuranosyl)-imidazole which was cyclized to provide the corresponding anhydronucleoside 5,5′-anhydro-4-nitro-5-oxo-1-(2,3-O-isopropylidene-β-D-ribofuranosyl)imidazole. Sodium hydrosulfide treatment of 5-bromo-4-nitroimidazole nucleoside provided 5-mercapto-4-nitro-1-β-D-ribofuranosylimidazole 5-sodium salt which was alkylated with E-1,5-diiodopent-1-ene to yield 5-(E-1-iodo-1-penten-5-yl)thio-4-nitro-1-β-D-ribofuranosylimidazole. The corresponding iodine-125-labeled compound was prepared similarly using radiolabeled diiodopentene. The 5-bromo-4-nitroimidazole, 5-mercapto-4-nitroimidazole, and 5-iodopentenylthio-4-nitroimidazole nucleosides were cytotoxic to Molt-3 cells in vitro at concentrations higher than 10 μg/mL. The radiolabeled 5-iodopentenylthio-4-nitroimidazole nucleoside showed 2-fold higher uptake in a rapidly growing tumor as compared to uptake in a relatively slower growing tumor in mice.     

Precision measurement ofK-shell fluorescence yields in actinide elements

High-precision measurements ofK Auger electron andK x-ray intensities have been made for several transuranium elements and these have been used to determineK-shell fluorescence yields (ω _K ). The electron spectra were measured with a cooled Si(Li) spectrometer and the photon spectra were taken with Ge(Li) diodes. Very thin mass-separated samples of nuclides, which decay predominantly by electron capture, were used in the present experiments. From our present measurements the following values ofK- shell fluorescence yield have been obtained: Np, 97.2±0.3%; Pu, 97.2±0.4%; Cm, 97.1 ±0.6%; Bk, 97.1±0.4%; Cf, 97.3±0.4%; and Es, 97.2±0.5%. These numbers indicate that theK-fluorescence yield for elements in theZ=93 toZ=99 region remains constant within the experimental error. The weighted average of these numbers is 97.19% with external error of 0.03% and internal error of 0.17%. This value is in excellent agreement with known theoretical calculations.     

Effect of wafer thinning methods towards fracture strength and topography of silicon die

This paper characterizes die damage resulting from various wafer thinning processes. Die fracture strength is measured using ball breaker test with respect to die surface finish. Further study on surface roughness and topography of each surface finish is obtained by atomic force microscopy (AFM) and scanning electron microscopy (SEM) techniques. Stress relief process with 25 μm removal is able to strengthen 100 μm wafer by 20.4% using chemical wet etch and 75 μm wafer by 36.4% with plasma etch. Relatively, plasma etching shows higher fracture strength and flexibility compared to chemical wet etch. This is due to topography of the finished surface of plasma etch is smoother and rounded, leading to a reduced stress concentration, hence improved fracture strength.     

A New Method for the Syntiiesis of 1-Aryl Phthalazines

A simple versatile method for the conversion of 1 -aroyl-2-(substituted benzylidene)-hydrazines to 1-aryl-phthalazines using polyphosphate ester (PPE) is described.