Dissoziative ionisierung von 2-trimethylsilyl-1-phenoxyethan. Nachweis des nicht-klassischen ethylen-trimethylsilanium-ions in der gasphase

The mass spectrometric investigation of specifically deuterium and ¹³C labelled 2-trimethylsilyl-l-phenoxyethanes proves that the dissociative ionization of β-silyl-substituted ethane derivatives (loss of PhO^?; p-CH₃C₆H₄O^?; and C₄H^?₉ from PhOCH₂CH₂SiMe₃, p-MeC₆H₄OCH₂CH₂SiMe₃ and CH₃CH₂CH(CH₃)CH₂-CH₂SiMe₃, respectively) yields the non-classical bridge ethylene trimethylsilanium ion and not the open-chain isomer. Other stable C₅H₁₃Si^+? ions, characterised by collisional activation mass spectrometry, are the dimethyl n-propyl silicenium ion and the l-trimethylsilyl ethyl cation, both generated from the molecular ions of CH₃CH₂CH₂Si(Cl)Me₂ and CH₃CH(Cl)SiMe₃ via unimolecular loss of Cl^?.     

Chelataustauscher auf Oxinbasis, 2. Mitt.: Zur Theorie der Komplexbildung im Chelataustauscher

Zusammenfassung Durch Messung der Verteilungskoeffizienten wird der Nachweis erbracht, daß Chelataustauscher durch Zusatz von Metalloxinaten, z. B. von Al- und Ba-Oxinat, während der Kondensation der Harze selektiver gemacht werden können. In dieser Arbeit werden die pH-lg _ex-kurven verschiedener Oxinatharze diskutiert. Die Form der Kurven wird aus dem Zusammenwirken von Komplexbildung, Donnan-Verteilung und Austauschvorgängen mit Carboxylgruppen abgeleitet. Die Steigungen der pH-lg _ex-kurven werden als Maß für die mittlere Ligandenzahl verwendet. Die Selektivität der Austauscher wird durch die pH₁₀₀-Werte charakterisiert. Damit wird der Nachweis erbracht, daß die sterische Anordnung des Oxins im Harz für die Selektivität mitverantwortlich ist.

---

By measuring the distribution coefficients it is shown that the selectivity of chelate resins can be raised by adding metaloxinates of Al and Ba, e.g., during the condensation. The pH-lg _ex-curves of various oxinate resins are discussed in this paper. The shape of the curves is derived from the interaction between complex formation, Donnan-distribution and exchange with carboxylic groups. The slope of the pH-lg _ex-curves is used as measure for the average ligand number. The selectivity of the resins is characterized by the pH₁₀₀ (pH value at _ex=100). From these experiments it follows conclusively, that the steric arrangement of the oxine in the resin is responsible for the selectivity.

---

---

Mit 8 Abbildungen

---

1. Mitt. (s. S. 1050) wird im folgenden I genannt.     

New Entrance Optics for Solar Spectral UV Measurements

The investigation of the impact of solar UV radiation on the biosphere requires spectral measurements of solar UV radiation of high accuracy. However, the accuracy of current measurements is limited, and this can partly be attributed to the entrance optics of the instruments used for these examinations. The angular response of spectro-radiometers measuring spectral global UV irradiance should be given by the cosine of the incidence angle. In-tercomparison campaigns have shown that deviations from this ideal cosine response lead to uncertainties in solar measurements of more than 10%. Here we present recently developed entrance optics that reduce these uncertainties to ±4% in the UV. The new entrance optics have been characterized with respect to their angular response, transmission, weather durability, fluorescence and dependence of the angular response on wavelength and polarization. Solar spectroradiometric measurements carried out with the new optics were compared with simultaneously performed measurements of a second spectroradiometer that was equipped with a conventional diffuser. The deviations of up to 12% between both systems are quantitatively explained to within 3%.     

Über die Störung des Morphiumnachweises bei der dünnschicht-chromatographischen Untersuchung von Raucherurinextrakten durch Nicotin

90% of the alkaline extracts contained substances giving positive reaction with iodoplatinate and Dragendorff reagents. One of these could be identified as nicotine. Methods for differentiating beween morphine and nicotine are mentioned and it is pointed to the possibility of erroneous results in the thin-layer chromatographic investigation of urinary extracts of smokers of basic pharmaceuticals.     

Photophysics and redox behavior of chiral transition metal polymers

The absorption and emission spectra, excited-state lifetimes, quantum yields, and electrochemical measurements have been obtained for a new series of chiral complexes based on three different chiral 2,2':6',2' '-terpyridine ligands, (-)-ctpy, (-)-[ctpy-x-ctpy], and (-)-[ctpy-b-ctpy], with one, two, or multiple Ru metal centers. The room-temperature absorption and emission maxima of [[((-)-ctpy)Ru]-(-)-[ctpy-b-ctpy]-[Ru((-)-ctpy)]](PF(6))(4) and ((-)-[ctpy-b-ctpy])-[[Ru((-)-[ctpy-b-ctpy])](PF(6))(2)](n) were shifted to lower energies and also exhibited significantly longer luminescence lifetimes when compared to [Ru((-)-ctpy)(2)](PF(6))(2), [[((-)-ctpy)Ru]-(-)-[ctpy-x-ctpy]-[Ru((-)-ctpy)]](PF(6))(4), and ((-)-[ctpy-x-ctpy])-[[Ru((-)-[ctpy-x-ctpy])](PF(6))(2)](n). In terms of their electrochemical behavior, all of the complexes studied exhibited one Ru-centered and two ligand-centered redox waves and the [[((-)-ctpy)Ru]-(-)-[ctpy-x-ctpy]-[Ru((-)-ctpy)]](PF(6))(4), ((-)-[ctpy-x-ctpy])-[[Ru((-)-[ctpy-x-ctpy])](PF(6))(2)](n), and ((-)-[ctpy-b-ctpy])-[[Ru((-)-[ctpy-b-ctpy])](PF(6))(2)](n)() complexes were found to electrodeposit upon ligand-based reduction. The difference between the formal potentials of the Ru-centered and the first ligand-centered (least negative) waves corresponded linearly with the changes in the observed emission energies. The shifts in energy are discussed using a particle-in-a-box model, and the luminescence lifetimes are discussed in terms of the structure of the excited-state manifold.     

Efforts to expand the genetic alphabet: identification of a replicable unnatural DNA self-pair

Six unnatural nucleotides featuring fluorine-substituted phenyl nucleobase analogues have been synthesized, incorporated into DNA, and characterized in terms of the structure and replication properties of the self-pairs they form. Each unnatural self-pair is accommodated in B-form DNA without detectable structural perturbation, and all are thermally stable and selective to roughly the same degree. Furthermore, the efficiency of polymerase-mediated mispair synthesis is similar for each unnatural nucleotide in the template. In contrast, the efficiency of polymerase-mediated self-pair extension is highly dependent on the specific fluorine substitution pattern. The most promising unnatural base pair candidate of this series is the 3-fluorobenzene self-pair, which is replicated with reasonable efficiency and selectivity.     

Wafer thickness optimization for silicon solar cells of heterogeneous material quality

In this Letter, we introduce a method of calculating the optimal wafer thickness for silicon solar cells with multicrystalline bulk material. The optimal thickness depends on the relation of bulk recombination to surface recombination and the light trapping. For multicrystalline silicon bulk recombination strongly varies laterally and with injection level, which complicates the calculations. A thickness optimization using the “Efficiency Limiting Bulk Recombination Analysis” (ELBA) takes all these effects correctly into account. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The effect of artifacts on dependence measurement in fMRI

The study of effective connectivity by means of neuroimaging depends on the measurement of similarity between activity patterns at different locations in the brain, without necessarily presupposing a particular model for this dependence. When these interactions are measured using functional magnetic resonance imaging (fMRI) techniques, however, imaging and physiological artifacts create patterns of dependence that may be unrelated to cortical activity. We demonstrate some of these effects through the measurement of short-range dependencies present in fMRI scans of the primary visual cortex (V1) in the anaesthetized macaque monkey. High-field (4.7 T) fMRI scans were conducted to measure responses based on the blood oxygen level-dependent contrast mechanism, during periods of no sensory stimulation and of visual stimulation with rotating polar-transformed checkerboard gratings. Dependence between the haemodynamic activity at different spatial locations (i.e., different voxels) was measured using correlation, mutual information and functional covariance. Particular attention was paid to understanding the sources of spurious dependence that may be observed during such investigations. Two main effects were detected: (a) short-range correlations introduced by the process of image reconstruction and (b) perturbations in the haemodynamic response caused by breathing. The image reconstruction artifacts were shown to create an artificially high short-range dependence in the readout direction of the scan, and the breathing artifacts caused enhanced short-range dependence in both the readout and phase-encode directions. Additional dependence in the phase-encode direction due to image-ghosting is also possible but will not be discussed in this report, as it can be alleviated by fine adjustment of preemphasis (elimination of eddy currents). A technique is described for removing breathing artifacts, and the effect of breathing on the apparent dependence between voxels is illustrated. The correlation of haemodynamic activity with the stimulus was found to be affected by breathing, although this effect can be neutralised by averaging the haemodynamic responses over many repetitions of the stimulus. Nonetheless, patterns of dependent activity between voxels may be lost in this averaging process, which makes the removal of breathing artifacts necessary if statistical dependence and the study of effective connectivity is the primary aim of an investigation.