Single-crystal structures of polyphenylene dendrimers

A series of first-generation polyphenylene dendrimers based on three different cores were prepared by Diels-Alder cycloaddition and their single-crystal structures were determined. Consisting exclusively of interlocked, twisted phenyl rings, these polyphenylene nanostructures have exciting structural and dynamic properties. Single crystals of dendrimers, suitable for X-ray structure analysis, were grown from different solvent mixtures by slow evaporation at room temperature. It should be pointed out that one of the described polyphenylene dendrimers represents up to now the biggest oligophenylene nanostructure from which crystallographic data is available.     

Quantitative depth profiling in glow discharge spectroscopies – A new deconvolution technique to separate effects of an uneven erosion crater shape

An algorithm is presented as a concept for the quantification in direct current and radiofrequency glow discharge (GD) modes for GD optical emission spectroscopy. The algorithm is divided into excitation and sputtering part and thus it is possible to distinguish between the different excitation processes and to consider equivalent sputtering crater formations in both modes. Intensity-time profiles are affected corresponding to the method by several effects. One important effect is that sputtering occurs at a single time in different depths because of curved crater bottoms, this is usually called crater effect. The main purpose is to introduce an iterative deconvolution technique which for the quantification numerically takes into account the curved sputtering crater bottom. Input data for the deconvolution technique are the calibrated mass-time profile, the partial densities of the sample constituents and the measured final shape of the sputtering crater. Using a relatively simple model for ion sputtering the deconvolution technique improves iteratively the calculated layer structure by means of information on crater formation. The mathematical handling is illustrated for the quantification of a depth profile of a multilayer sample of ten 100 nm layers. The resulting concentration-depth profile reflects excellently the real elemental distribution of the multilayer system.     

Glow discharge mass spectrometry

Over the past twenty years or so, glow discharge mass spectrometry (GDMS) has become the industry standard for the analysis of trace elements in metals and semiconductors. A review of its history is followed by a picture of the present situation and a look to where the future may lie. Applications are summarised, including the ability of GDMS to offer depth-resolved data and non-conductor analysis, and the well-documented quantitative nature of the results is reviewed. The effects resulting from the physical properties of the analyte material are discussed at length. Finally, recent work such as fast flow sources and pulsed glow discharges is reviewed.     

Full multinuclear resonance analysis of 4-amino-1,1,2,2,9,9,10,10-octafluoro[2.2]paracyclophane

The complete assignment of 19F, 1H and 13C NMR spectra for a monosubstituted octafluoro[2.2]paracyclophane derivative is described for the first time. The unambiguous assignments were achieved through the combination of 19F--1H HOESY, 1H COSY and 19F COSY techniques and then further confirmed employing a complementary approach using a Karplus-dependent 3JCF interaction. Interesting aspects of the coupling patterns for various JHH, JHF, JCF and JFF interactions are also discussed.     

Multi-element trace analysis of tungsten

Investigations carried out in order to determine traces of 25 elements in tungsten in the lower g/g range are reported on. Atomic absorption spectrometry and plasma atomic emission spectrometry as well as solution photometry and activation analysis were the main techniques used.     

Indirect determination of the sum of chelons in drinking- and ground-waters by anodic stripping voltammetry

The complexing ligand EDTA can be determined as its complex with bismuth by indirect anodic stripping voltammetry down to 0.1 μg/L without a concentration step. Interfering copper and excess bismuth have to be removed by cation exchange, although in presence of these metals EDTA can be determined down to 0.5 μg/L only. If NTA, EDTA, and DTPA are present simultaneously, the accumulation curves for the corresponding bismuth-complexes can overlap, preventing a separate determination of the three chelons. Due to the interaction of NTA and DTPA with soil normally only EDTA is present in ground-waters. Similarly, EDTA also dominates in surface-waters. Thus it seems to be sufficient to determine the sum of the three chelons as EDTA (index of bismuth-complexation) using suitable electrochemical conditions.     

Untersuchungen zurFriesschen Verschiebung von Estern derortho- undpara-Methoxybenzoesäure

TheFries rearrangement of different methoxy benzoates has been investigated. Frompara-methoxy benzoates the corresponding hydroxy-4-methoxy benzophenones could be obtained in good yields by treatment withLewis acids (especially TiCl₄) in nitromethane at 20°C (4-hydroxy derivatives) or without solvent at 120°C (2-hydroxy derivatives). Under the same conditions only demethylation occurs withortho-methoxy benzoates leading to the corresponding salicylates. Small amounts of hydroxy-2-methoxy benzophenones were obtained by treatment with polyphosphoric acid.

     

The Lewis basicity of the [Pt3(μ-CO)3(PR3)3] clusters and the X-ray crystal structure of [{ZnI2}{Pt3(μ-CO)3(PPh(i-Pr)2)3}]

The cluster compounds [Pt₃(μ-CO)₃(PR₃)₃] act as Lewis bases towards the metal halides of Group XI, MX, Group XII, MX₂, and Group XIII, MX₃, to form cluster compounds of the composition [{MX_n}{Pt₃(μ-CO)₃(PR₃)₃}]. The X-ray crystal structure, NMR and IR data are given for the compound [{ZnI}{Pt₃(μ-CO)₃(PPh(i-Pr)₂)₃}].