Isomerization and fragmentation reactions of gaseous phenylarsane radical cations and phenylarsanyl cations. A study by tandem mass spectrometry and theoretical calculations

The unimolecular reactions of radical cations and cations derived from phenylarsane, C6H5AsH2 (1) and dideutero phenylarsane, C6H5AsD2 (1-d2), were investigated by methods of tandem mass spectrometry and theoretical calculations. The mass spectrometric experiments reveal that the molecular ion of phenylarsane, 1*+, exhibits different reactivity at low and high internal excess energy. Only at low internal energy the observed fragmentations are as expected, that is the molecular ion 1*+ decomposes almost exclusively by loss of an H atom. The deuterated derivative 1-d2 with an AsD2 group eliminates selectively a D atom under these conditions. The resulting phenylarsenium ion [C6H5AsH]+, 2+, decomposes rather easily by loss of the As atom to give the benzene radical cation [C6H6]*+ and is therefore of low abundance in the 70 eV EI mass spectrum. At high internal excess energy, the ion 1*+ decomposes very differently either by elimination of an H2 molecule, or by release of the As atom, or by loss of an AsH fragment. Final products of these reactions are either the benzoarsenium ion 4*+, or the benzonium ion [C6H7]+, or the benzene radical cation, [C6H6]*+. As key-steps, these fragmentations contain reductive eliminations from the central As atom under H-H or C-H bond formation. Labeling experiments show that H/D exchange reactions precede these fragmentations and, specifically, that complete positional exchange of the H atoms in 1*+ occurs. Computations at the UMP2/6-311+G(d)//UHF/6-311+G(d) level agree best with the experimental results and suggest: (i) 1*+ rearranges (activation enthalpy of 93 kJ mol(-1)) to a distinctly more stable (DeltaH(r)(298) = -64 kJ mol(-1)) isomer 1 sigma*+ with a structure best represented as a distonic radical cation sigma complex between AsH and benzene. (ii) The six H atoms of the benzene moiety of 1 sigma*+ become equivalent by a fast ring walk of the AsH group. (iii) A reversible isomerization 1+<==>1 sigma*+ scrambles eventually all H atoms over all positions in 1*+. The distonic radical cation 1*+ is predisposed for the elimination of an As atom or an AsH fragment. The calculations are in accordance with the experimentally preferred reactions when the As atom and the AsH fragment are generated in the quartet and triplet state, respectively. Alternatively, 1*(+) undergoes a reductive elimination of H2 from the AsH2 group via a remarkably stable complex of the phenylarsandiyl radical cation, [C6H5As]*+ and an H2 molecule.     

Automatic analysis of multiplex ligation-dependent probe amplification products (exemplified by a commercial kit for prenatal aneuploidy detection)

For use in routine prenatal diagnostics, we developed software and methods for automatic aneuploidy detection based on a commercial multiplex ligation-dependent probe amplification (MLPA) kit. Software and methods ensure a reliable, objective, and fast workflow, and may be applied to other types of MLPA kits. Following CE of MLPA amplification products, the software automatically identified the peak area for each probe, normalized it in relation to the neighboring peak areas of the test sample, computed the ratio relative to a reference created from normal samples, and compensated the ratio for a side effect of the normalization procedure that scaled all chromosomally normal DNA peak areas slightly up or down depending on the kind of aneuploidy present. For the chromosomes 13, 18, 21, X, and Y, probe reliability weighted mean ratio values and corresponding SDs were calculated, and the significance for being outside a reference interval around ratio 1.0 was tested. p < or = 1% suggested aneuploidy and 1 < p < or = 5% suggested potential aneuploidy. Individual peaks, where the normalized area was situated more than 4 SD from the corresponding reference, suggested possible partial deletion or gain. Sample quality was automatically assessed. Control probes were not required. Having used the software and methods for two years, we conclude that a reliable, objective, and fast workflow is obtained.     

Spectralapparat

Ohne Zusammenfassung     

An investigation of centrifugal distortion in the microwave spectrum of formamide

Measurements of the microwave spectrum of formamide have been extended in order to account accurately for the effects of centrifugal distortion. A total of 22 new transitions involving J ≤ 29 have been measured for ¹⁴NH₂¹²CH¹⁶O in the ground vibrational state. Combined with previous observations, these transitions have been fit to a model containing five quartic distortion terms and seven sextic terms with a rms deviation of 64 kHz. A large number of resolved quadrupole shifts were fit with an rms deviation of 42 kHz. The remainder of the spectrum for J ≤ 30 has been calculated with standard deviations less then 3 MHz. Correct weighting of the observed transitions has been found to be important.     

THE NATURE OF ULTRAVIOLET LIGHT-INDUCED STRAND BREAKAGE IN DNA CONTAINING BROMOURACIL

Abstract— Single-strand breaks are produced in the phosphodiester backbone of ultraviolet-light-irradiated 5–bromodeoxyuridine-containing DNA (BU-DNA) after treatment with alkali. No radiation dependent breakage is observed in thymine-containing DNA (thy-DNA). The relative yields of breaks terminated by 5'-hydroxyl and 5'-phosphate groups was determined by measuring the rate of phosphorylation achieved with polynucleotide kinase in BU-DNA single strands before and after treatment with alkaline phosphatase. The ratio of 5'-phosphate to 5' hydroxyl groups ranged from 2.3 to 2.9 in different experiments. When cysteamine was present during irradiation no new end groups were produced.
In order to identify the nucleoside(s) at the 5'-termini, phosphate groups were removed with alkaline phosphatase and the 5'-hydroxyl groups were phosphorylated with polynucleotide kinase. Electrophoresis of enzymatic digests showed a single ³²P-labeled component migrating more rapidly than any of the four usual 5'-mononucleotides. Upon column chromatography this component resolved into a major peak coincident with 5'-dUMP and a lesser unidentified constituent. No 5'-dBUM³²P was observed among these nucleotides.     

Interparticle forces in silica nanoparticle agglomerates

To improve the understanding of the poor dispersability of fumed silica nanoparticle agglomerates, the stability of highly defined agglomerated model particles was investigated. The high temperature synthesis conditions for fumed silica were simulated by tempering. Along with electron-microscopical analysis of the sintering necks, the interparticle forces were investigated by energy resolved fragmentation analysis based on low pressure impaction. At temperatures above 1,000 °C the fragmentability of the agglomerates rapidly decreased while the energy necessary for fragmentation increased. The development of sintering necks was observed for temperatures exceeding 1,300 °C. Comparison of the experimental data with the fragmentation behaviour of a commercially produced fumed silica indicated solid state contacts (sintering necks) as being most numerous in the agglomerates resulting in limited fragmentability.