Separation of non UV-absorbing cations by capillary electrophoresis

Summary A new buffer system for the separation of cations with capillary electrophoresis using indirect UV-detection is described. p-Aminopyridine can be used in the wide pH-range between 3 and 10. High-speed separations of positively charged non-UV absorbing ions are possible. Separation of ions with similar mobilities can be achieved by the addition of complexation reagents. The separation of potassium and ammonium is possible either with the addition of crown ether or at high pH-values. Transition metals can be separated by adding 2-hydroxybutyric acid to the buffer.Dedicated to Professor Dr. Wilhelm Fresenius on the occasion of his 80th birthday     

Neue Spiroverbindungen aus Cyclophosphazenen und Cyclodi[phosphadiazan]en

New Spiro Compounds from Cyclophosphazenes and Cyclodi[phosphadiazanes] Chlorocyclophosphazenes (Cl₂P = N)₃ and (Cl₂p = N)₄ react with dihydrazidophosphoric acid derivatives in THF in the presence of triethylamine to give the spirocyclic compounds Cl₄N₃P₃(NHN(CH₃))₂P(S)OC₆H₅, Cl₆N₄P₄(NHNH)₂P(S)OC₆H₅. Constitutions have been confirmed by MS, NMR, IR and elemental analysis.     

Automatische Analyse und Simulation von NMR-Spektren

Analytical and Bioanalytical Chemistry -     

N(nPr)4[B5O6(OH)4][B(OH)3]2 and N(nBu)4[B5O6(OH)4][B(OH)3]2: Clathrates with a diamondoid arrangement of hydrogen-bonded pentaborate anions

Single-crystal X-ray structure analyses of N(nPr)₄[B₅O₆(OH)₄][B(OH)₃]₂,1, and N(nBu)₄ [B₅O₆(OH)₄][B(OH)₃]₂,2, reveal that these materials are novel clathrates, the isotypic host structures of which are three-dimensional assemblies of hydrogen-bonded [B₅O₆(OH)₄]^– ionsand B(OH)₃ molecules. The assembly of only the pentaborate anions is a distorted (i.e., along [102] elongated) fourconnected diamond-related network. The N(nPr) ₄ ⁺ and N(nBu) ₄ ⁺ ions are trapped within the complex three-dimensional channel systems of the host frameworks. Both1 and2 crystallize monoclinically with space groupP2₁/c andZ=4. The cell constants are:1:a=13.592(5),b=12.082(2),c=17.355(6) Å, =106.60(2)° (298K);2:a=13.874(3),b=12.585(1),c=17.588(4) Å, =107.04(1)° (238 K). The results obtained by both¹¹B and¹³C MAS NMR spectroscopy are discussed. Thermogravimetric studies under a flowing inert-gas atmosphere suggest that water, stemming from polycondensation of the hydrous borate species, is released from the clathrates at ca. 443 K (1) and 398 K (2) before the decomposition of the organic cations starts at ca. 603 K (1) and 603 K (2).Author for correspondence. Supplementary Data relating to this article are deposited with the British Library as supplementary publication No. SUP 82172 (82 pages).     

Über den Anionenaufbau wäßriger Tetra-n-propyl- und Tetraethylammoniumsilicatlösungen

On the Anion Constitutions of Aqueous Tetra-n-propylammonium and Tetraethylammonnium Silicate Solutions The constitution of the silicate anions present in 0.1 M to 3 M tetrapropylammonium-(TPA-) and tetraethylammonium-(TEA-)silicate solutions with molar TPA/Si ratios of 3, 1 and 0.6 and TEA/Si ratios of 3 and 1 is investigated by means of trimethylsilylation. Up to 16 different oligomeric silicate anions are detected and estimated quantitively. Type and quantitative dis-tribution of the silicate anions are very similar in diluted 0.1 M TEA- and TPA-silicate solutions. Concentrated TEA-silicate solutions contain preferably Si₆O₁₅^6? anions whereas concentrated TPA-silicate solutions are characterized by a broad distribution of different oligomeric silicate anions. The anion distribution of TPA- and TEA -silicate solutions is compared with the results of tetramethyl- and tetrabutylammonium silicate solutions studied previously.