Lanthanoid-nickel-phosphides with ThCr2Si2-type structure

The new compounds YNi₂P₂ and LnNi₂P₂ (Ln = La, Ce, Pr, Nd, Sm, Tb, Dy, Ho, Er, Tm) were prépared by sintering the elemental components in silica tubes. Well-developed crystals were obtained using tin as a flux. They crystallize with the ThCr₂Si₂ (CeGa₂Al₂)-type structure which was refined from single-crystal X-ray data for EuNi₂P₂ to a conventional R value of 0.049 for 118 unique structure factors. While the P atoms in formally isotypic EuCo₂P₂ are isolated from each other, they form pairs in EuNi₂P₂. This results in a different $\text{c}\text{a}$ ratio and an entirely different bonding situation. A comparison of cell volumes shows that Eu in EuNi₂P₂ has an intermediate valence.     

Selective modification of the 2-position of pyridoxol

Pyridoxol, protected by acetylation of the hydroxyl groups, has been converted to its N-oxide which upon reaction with perfluoroacetie anhydride yields a 2-nor-2-hydroxymethylpyridoxol derivative as an intermediate. This compound undergoes acyl migration from the 3-position. Protection of the pyridoxol hydroxyls by benzylalion followed by the same treatment yields the unrearranged α²-hydroxy derivative. This compound has been converted to a series of α²-substituted pyridoxols (X = -Cl, -Br, -OCOCH₃, -OCH₃, -OC₂H₅).     

Laser desorption of DNA oligomers larger than one kilobase from cooled 4-nitrophenol

A unique matrix system consisting mostly of 4-nitrophenol has shown to be very effective for matrix-assisted laser desorption/ionization time-of-flight mass spectrometric analysis of large DNA oligomers when a cooled sample stage was used to prevent the sublimation of this matrix under vacuum. Using this 4-nitrophenol matrix with UV laser desorption, detection of picomole quantities of DNA oligomers containing up to approximately 800 nucleotides was routinely achieved. The effectiveness of this matrix was further demonstrated by the observation of a double-stranded DNA oligomer larger than 1000 base pairs, seen as a denatured single-stranded species, with a molecular ion mass exceeding 300 000 Da. The potential applications of 4-nitrophenol as a matrix for DNA sizing are discussed.     

Emissionsspektrometrische Analyse von Roheisen

Zusammenfassung Die spektrometrische Analyse von weiß erstarrtem Roheisen (auf C, Si, Mn, P, S, Cu) ist mit der gleichen Anregung und in der gleichen Funkzeit wie diejenige von Stahl möglich. Eine spezielle Kalibriertechnik mit Stahlproben garantiert ein ausreichend reproduzierbares und richtiges Resultat in relativ kurzer Zeit (20 sec).

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Emission-spectrometrical analysis of pig iron

The conditions of pig iron analysis by using a direct reading spectrometer for routine determination of C, Si, Mn, P, S and Cu, the influence of sampling and a new calibration technique of the instrument are described. The whole time needed for complete spectrometrical analysis is about 20 sec.

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Wir sind Herrn T. Nientiedt für zahlreiche Anregungen und Diskussionen zu Dank verpflichtet.     

Trimethylsilylverbindungen der Vb-Elemente. VI. Synthese,Molekül- und Kristallstruktur des Tetrakis(trimethylsilyl)distibans im Vergleich mit Tetraphenyldistiban

Trimethylsilyl Derivatives of Vb-Elements. VI. Synthesis, Molecular and Crystal Structure of Tetrakis(trimethylsilyl)distibine Compared with Tetraphenyldistibine Tetrakis(trimethylsilyl)distibine already isolated by Breunig et al. [9] from cleavage reactions of tris(trimethylsilyl)stibine may also be obtained in high yields from lithium bis(trimethylsilyl)antimonide · 2THF and 1,2-dibromoethane in n-pentane. This compound intensely red in the solid state, but only slightly yellow in solution or in the melt crystallizes in the monoclinic space group P2₁/c with a = 680.6(1); b = 1672.8(2); c = 1190.0(1) pm; β = 119.01(5)°; Z = 2 at +20°C. An X-ray structure determination (R = 0.017) shows the bis(trimethylsilyl)-stibino groups to be arranged in a transoid position. Characteristic bond lengths and angles are: Sb? Sb 286.7(1); Sb? Si 259.4 pm; Si? Sb? Si 94.46(3); Sb? Sb? Si 98.68(3) and 94.43(3)°. As in similiar 2,2′,5,5′-tetramethyldistibolyl published recently by Ashe III et al. [8] this crystal structure, too, is characterized by a nearly linear sequence of Sb? Sb groups. Compared with the sum of van-der-Waals radii the intermolecular Sb-Sb contact in such a chain is shortened from 440 to 399 pm. This probably allows electronic interactions of unknown type responsible for the colour of the crystals. In keeping with this assumption an analogous formation of chains is not found in solid, only yellow tetraphenyldistibine 5 the structure of which has already been studied by Rehder et al. [44].