An Alternative to Automatic Titration

Automatic titrators are designed to do exactly what a lab-technician used to do. Much more sophisticated automation of volumetry is possible. Omegaphoresis [3] in buffer-free [2] sample solutions automatically creates a stationary multiple component titration curve or zoned pattern with normalized concentrations of each separated species. An automatic measurement of each zone length yields their quantity. Simultaneous automatic detection of all the zones in a 10–20 component solution in less than 2 minutes, with a precision of ±2%, a required amount of the order of less than one nanomol and a resolution of ±pK < 0.01 replaces acid-base, complexometric, and certain types of redox-titrimetry. An option of the method allows identification of the components as well.     

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.     

Markierungsexperimente zur fragmentierung von 1,2,3-thiadiazolen

The generation of thiirenes in the thermal and photochemical nitrogen elimination of 1,2,3-thiadiazoles is discussed in relation to oxirene formation. Isotope labelling experiments were performed with 4-phenyl-[4-¹³C]-1,2,3-thiadiazole ( 7 ) as the substrate.     

Reduction of 1,4-dichlorobut-2-yne by titanocene to a 1,2,3-butatriene. Formation of a 1-titanacyclopent-3-yne and a 2,5-dititanabicyclo[2.2.0]hex-1(4)-ene

The 2,5-dititanabicyclo[2.2.0]hex-1(4)-ene (bis-titanocene-mu-(Z)-1,2,3-butatriene complex)3 is formed starting from [Cp2Ti(eta2-Me3SiC2SiMe3)] by in situ generated titanocene and 1,4-dichlorobut-2-yne via the 1-titanacyclobut-3-yne (2).     

A new look at rotational and vibrational excitation in the scattering of Li+ from N2 and CO at energies between 4 and 17 eV

New experimental time-of-flight distributions are reported for Li⁺-N₂ and Li²-CO at two center-of-mass energies of about 8 and 16 eV and large scattering angles θ_lab ? 120°. The Li⁺-N₂ spectra show two widely spaced maxima, whereas the Li⁺-CO spectra show two and sometimes three maxima. The results are consistent with the model of rotational rainbows, and have also been analyzed in terms of an impulsive model involving collisions with the individual atoms of the molecules with energy-dependent masses. Classical trajectories for a simple model potential reveal only small contributions from vibrational excitation.     

Intramolekulare Cyclisierung von Aminofluorsilanen

Aminofluorosilanes react with lithiated amines undergoing LiF-elimination and substitution (1). The acyclic silicon-nitrogen-compound2 is isolated in the reaction with a difluorosilane after renewed lithiation.2 is cyclisated in the reaction with butyllithium by butane- and LiF-elimination (3). Aminofluorosilanes with bulky (4) or mesomeric stabilized (5) ligands form stable lithioaminofluorosilanes, which react with fluorosilanes giving substitution products (6, 7).6 and7 react with the lithium salt oftert-butylamin in a molar ratio of 12 to give8 and9 by intramolecular cyclisation.—The mass,¹H and¹⁹F nmr spectra of the compounds are reported.     

Hexaphosphapentaprismane: a new gateway to organophosphorus cage compound chemistry

Several independent synthetic routes are described leading to the formation of a novel unsaturated tetracyclic phosphorus carbon cage compound tBu4C4P6 (1), which undergoes a light-induced valence isomerization to produce the first hexaphosphapentaprismane cage tBu4C4P6 (2). A second unsaturated isomer tBu4C4P6 (9) of 1 and the bis-[W(CO)5] complex 13 of 1 are stable towards similar isomerization reactions. Another starting material for the synthesis of the hexaphosphapentaprismane cage tBu4C4P6 (2) is the trimeric mercury complex [(tBu4C4P6)Hg]3 (11), which undergoes elimination of mercury to afford the title compound 2. Single-crystal X-ray structural determinations have been carried out on compounds 1, 2, 9, 11, and 13.     

Multiplexed hybridizations of positively charge-tagged peptide nucleic acids detected by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Peptide nucleic acid (PNA) is a novel class of DNA analogues in which the entire sugar-phosphate backbone is replaced by a pseudopeptide counterpart. Owing to its neutral character and the consequent lack of electrostatic repulsion, PNA exhibits very stable heteroduplex formation with complementary nucleic acid that is essentially ionic strength independent and enables hybridization under minimum salt conditions. This feature as well as its superior ion stability and easy ionization compared to DNA renders PNA very attractive for hybridization-based matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) applications. We have developed an approach to DNA characterization that takes advantage of multiplexed PNA hybridizations analyzed by MALDI-TOFMS. Our motivation was the further development of oligonucleotide fingerprinting, an efficient technique for cDNA and genomic DNA library characterization. Through positive 'charge-tagging' of PNA the efficiency of detection in MALDI-TOFMS was considerably enhanced permitting an unparalleled degree of multiplexing. Results from the simultaneous hybridization of 21 charge-tagged PNA hexamer oligonucleotides showed that genomic DNA and cDNA clones are successfully characterized on the basis of their hybridization profiles. The degree of multiplexing achieved may render a significant increase in throughput and hence efficiency of oligonucleotide fingerprinting possible.