Structural insights into aluminum chlorofluoride (ACF)

The structure of the very strong solid Lewis acid aluminum chlorofluoride (ACF, AlCl(x)F(3-x), x = 0.05-0.3) was studied by IR, ESR, Cl K XANES, (19)F MAS NMR, and (27)Al SATRAS NMR spectroscopic methods and compared with amorphous aluminum fluoride conventionally prepared by dehydration of alpha-AlF(3) x 3H(2)O. The thermal behavior of both compounds was investigated by DTA and XRD. In comparison to ACF, amorphous AlF(3) prepared in a conventional way is not catalytically active for the isomerization reaction of 1,2-dibromohexafluoropropane, which requires a very strong Lewis acid. Both compounds are mainly built up of corner-sharing AlF(6) octahedra forming a random network. The degree of disorder in ACF is higher than in amorphous AlF(3). Terminal fluorine atoms were detected in ACF by (19)F NMR. The chlorine in ACF does not exist as a separate, crystalline AlCl(3) phase. Additionally, chlorine-containing radicals, remaining from the synthesis, are trapped in cavities of ACF. These radicals are stable at room temperature but do not take part in the catalytic reaction.     

Synthesis of primary amines: first homogeneously catalyzed reductive amination with ammonia

[reaction: see text] The synthesis of primary amines via reductive amination of the corresponding carbonyl compounds with aqueous ammonia is achieved for the first time with soluble transition metal complexes. Up to an 86% yield and a 97% selectivity for benzylamines were obtained in the case of various benzaldehydes by using a Rh-catalyst together with water-soluble phosphine and ammonium acetate. In the case of aliphatic aldehydes, a bimetallic catalyst based on Rh/Ir gave improved results.     

Experimental study of electrostatically stabilized colloidal particles: colloidal stability and charge reversal

We consider the interaction of colloidal spheres in the presence of mono-, di-, and trivalent ions. The colloids are stabilized by electrostatic repulsion due to surface charges. The repulsive part of the interaction potential Ψ(d) is deduced from precise measurements of the rate of slow coagulation. These "microsurface potential measurements" allow us to determine a weak repulsion in which Ψ(d) is of the order of a few k(B)T. These data are compared to ζ potential measured under similar conditions. At higher concentrations both di- and trivalent counterions accumulate at the very proximity of the particle surface leading to charge reversal. The salt concentration c(cr) at which charge reversal occurs is found to be always above the critical coagulation concentration c(ccc). The analysis of Ψ(d) and of the ζ potential demonstrates, however, that adsorption of multivalent counterions starts far below c(cr). Hence, colloid stability in the presence of di- and trivalent ions cannot be described in terms of a DLVO ansatz assuming a surface charge that is constant with regard to the ionic strength.     

Determination of heavy metals in suspended matter in the storage lake “Bitterfelder Muldestausee”

Dissolved and particulate trace elements have been determined in 400 samples of both the inflow and the outflow waters of the storage lake “Bitterfelder Muldestausse” in order to investigate the sedimentation of 22 elements transported by the highly polluted Mulde River, an affluent of the river Elbe. Inductively coupled plasma mass spectrometry (ICP-MS) has been used to analyse filtered water samples because of its multielemental capabilities, the excellent detection limits, the wide linear calibration range and the high speed of analysis. A special leaching procedure has been employed for the very low amounts of the suspended matter collected from each water sample. The dissolved material has been also analysed by ICP-MS. Testing of the procedure employed by the analysis of a standard reference material (SRM BCR 146) and use of the standard addition method has resulted in both a good precision (1–7%) and accuracy. Despite the wide variation in the composition of the suspended matter samples the concentrations of the heavy metals in sediment samples and in the suspended matter have been found to be comparable. A balance of sedimentation has been calculated based on the mean values of concentrations of all elements investigated in both the water and suspended matter samples of the inflow and outflow. Results from this first study show that the storage lake acts as a sedimentation trap for Zn, Cu, Pb, Ni, Cr, Cd, U and Co.     

Molecule formation in electrothermal atomizers: Interferences and analytical possibilities by absorption, emission and fluorescence processes

Summary The formation of stable diatomic molecules in graphite tube furnaces is described. It is also shown that the new isothermal evaporation techniques in AAS do not lead to complete dissociation of molecules with dissociation energies > 3–4 eV. Systematic errors of AA results follow.Systematic studies of the application of diatomic molecules (MX-type) for trace analysis of non-metals (X) were carried out. Many results are given for molecular absorption with electrothermal evaporation (MAS-ETE). Trace determinations in ng level (l samples) for F, Cl, Br, S and I and their anions are possible. Examples for real analysis are given.Principles of over-excitation for improvement of detection limits of non-metals are applied to diatomic molecules.The application of the non-thermal FANES excitation leads to the development of the new method MONES-ETE (molecular non-thermal emission spectrometry with electrothermal evaporation) with detection limits below 1 ng for F, Cl, Br using InX molecules.The application of the principle of laser excited fluorescence leads to the new method LAMOFS-ETE (laser excited molecular fluorescence with electrothermal evaporation) with the upto now best detection limits for F, Cl, Br at pg level using AlBr, InCl, MgF molecules.

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Molekülbildung in elektrothermischen Atomisatoren: Störungen und analytische Möglichkeiten durch Absorptions-, Emissions- und Fluorescenzprozesse

Zusammenfassung Es wird die Bildung von stabilen, vorwiegend 2-atomigen Molekülen in Graphitrohrküvetten beschrieben. Es wird festgestellt, daß auch die modernen isothermen Verdampfungstechniken bei Molekülen mit Dissoziationsenergien > 3–4 eV nicht zur vollständigen Dissoziation führen. Systematische Fehler von AA-Resultaten sind die Folge.Systematische Untersuchungen zur Anwendung 2-atomiger Moleküle vom MX-Typ (z. B. AlF) für die Spurenanalyse von Nichtmetallen (X) werden beschrieben. Umfangreiche Ergebnisse werden zur Molekülabsorption mit elektrothermischer Verdampfung (MAS-ETV) angeführt. Spurenbestimmungen im Nanogramm-Bereich (Mikroliter-Proben) sind möglich für F, Cl, Br, S und I bzw. deren Anionen.Prinzipien der Überanregung werden zur Verbesserung der Nachweisgrenzen von Nichtmetallen auf 2-atomige Moleküle angewendet. Die Anwendung der nichtthermischen FANES-Anregung führt zur Entwicklung der neuen Methode MONES-ETV (Molekül-nichtthermische Emissionsspektroskopie mit elektrothermischer Verdampfung) mit Nachweisgrenzen unterhalb des Nanogramm-Bereichs für F, Cl und Br durch InX-Moleküle. Die Anwendung des Prinzips der laserangeregten Atomfluorescenz führt zur neuen Methode LAMOFS-ETV (laserangeregte Molekülfluorescenzspektrometrie mit elektrothermischer Verdampfung) mit den bisher besten Nachweisgrenzen von einigen Picogramm für F, Cl, Br durch Anwendung der AlBr, InCl und MgF-Moleküle.

     

Zur Theorie des Exzitons in den Alkalihalogeniden

Following the many-body treatment of exciton byHaken andSchottky we represent the electronic polarization of the lattice induced by the excess electron and the hole in the Hamiltonian as well as in the wave function by introducing localized pair states and their coupling with the exciton particles. By application of a unitary transformation the pair states may be eliminated and one obtains the effective Schrödinger equation of an exciton consisting of particles dressed with polarization clouds. The coupling coefficients are determined by a minimum condition for the polarization energy. The effective interaction law between electron and hole and their effective masses are investigated explicitly. By transformation of the Schrödinger equation into a system of difference equations and solution of the corresponding secular equation one obtains an expression for the binding energy of the lowest exciton state in the alkali halides, which represents a connection of the “excitation” and “transfer” models. For the iodides of Na, K and Rb the binding energies were calculated using an approximative estimate for the various matrix elements involved. They are in good agreement with the experimentally observed energy differences between the first absorption peak and the small shoulder which indicates the position of the band edge.     

Proton spin relaxation of molecules adsorbed in NaY and NaPtY zeolite; The influence of adsorbed water on the distribution of atomic platinum

The longitudinal proton spin relaxation time T₁ of molecules adsorbed in commercial zeolites is predominantly caused by paramagnetic impurities, typically of the order of 0.1 wt% of iron. If only 1 wt% of platinum is introduced into the zeolite (as [Pt(NH₃)₄]²⁺), T₁ of water is enhanced up to one order of magnitude, as was shown in a preceding paper. The reason for this effect is that, under suitable thermal pretreatment of the Pt-exchanged zeolite, the Pt²⁺ ions are reduced by the ammonia to atomic platinum and part of the Pt atoms migrate preferentially to Fe³⁺ ions. Thus, Fe³⁺ ions, controlling T₁, are covered and up to 90% of paramagnetic sites for water is occupied by Pt atoms. In this paper, it is shown that Pt atoms preferentially migrate to Fe³⁺ ions only under the influence of water and that, therefore, various adsorbed organic molecules do not show the enhancement of T₁, unless the NaPtY zeolite is suitably pretreated with water before the organic molecules are adsorbed.     

Finding small somatic structural variants in exome sequencing data: a machine learning approach

Genetic variation forms the basis for diversity but can as well be harmful and cause diseases, such as tumors. Structural variants (SV) are an example of complex genetic variations that comprise of many nucleotides ranging up to several megabases. Based on recent developments in sequencing technology it has become feasable to elucidate the genetic state of a person’s genes (i.e. the exome) or even the complete genome. Here, a machine learning approach is presented to find small disease-related SVs with the help of sequencing data. The method uses differences in characteristics of mapping patterns between tumor and normal samples at a genomic locus. This way, the method aims to be directly applicable for exome sequencing data to improve detection of SVs since specific SV detection methods are currently lacking. The method has been evaluated based on a simulation study as well as with exome data of patients with acute myeloid leukemia. An implementation of the algorithm is available at https://github.com/lenz99-/svmod.     

Synthesis of silver nanoparticle necklaces without explicit addition of reducing or templating agents

Here we report that silver nanoparticle necklaces can be readily formed by treatment of colloidal silica with ammoniacal silver complex solution followed by washing, deposition and ageing. We investigate the morphology of the produced materials and elucidate the key variables that influence this promising new approach to one-dimensional nanostructuring.