Crystallisation Solvent Influence on the Crystal Structures of MnII and NiII Complexes with 2,6‐bis(1‐salicyloylhydrazonoethyl)pyridine,H4daps

Neutral manganese and nickel complexes of the empirical formulae Mn(H₂daps)(H₂O)_0.5 and Ni(H₂daps) · (H₂O)_1.5(CH₃CN) have been prepared by electrochemical syntheses. The structures of the complexes formed from solvents with different donor ability were investigated. Recrystallisation of Mn(H₂daps)(H₂O)_0.5 from pyridine and ethanol yields [Mn(H₂daps)(py)₂] 1 and [Mn(H₂daps)(C₂H₅OH) · (H₂O)] 2 . Slow evaporation of dichloromethane and methanol solutions of Ni(H₂daps)(H₂O)_1.5(CH₃CN) allows the isolation of single crystals of [Ni₂(H₂daps)₂] · CH₂Cl₂ 4 and [Ni₂(H₂daps)₂(CH₃OH)₂] · 3 CH₃OH · H₂O 5 , suitable for X‐ray diffraction studies. Recrystallisation of 4 from pyridine yields [Ni₂(H₂daps)₂(py)₂] · CH₂Cl₂ 6 , previously characterised by us. This study shows the versatility of the H₄daps ligand and the influence that the crystallisation solvent can have on the crystal structure of these complexes.     

Controlled cell aggregation in a pulsed acoustic field

Cell aggregation in ultrasonic resonators can be obtained in a few seconds. Hundreds even thousands of cells can be levitated in suspension and generate 2D or 3D aggregates. Nevertheless, the aggregation rate and the 2D or 3D configurations of the resultant aggregates are very difficult to control. This work reports on a novel way of generating and controlling particle and cell aggregates using pulsed ultrasound. This technique specifically explores (in addition to the ultrasound wave, frequency and amplitude) the time of ultrasound application, i.e. the number of pulses as well as the pulse repetition frequency. We demonstrate that with pulsed ultrasound, particles and/or cells levitate in suspension, as with continuous ultrasound, and the aggregation rate can be modified in a controlled manner. By carefully tuning the number of pulses and the repetition frequency, the 3-D and 2-D configurations of the aggregates can be selectively generated. In addition, pulsed ultrasound limits transducer heating, thus allowing for higher acoustic energies than those currently employed with continuous ultrasound.     

The impact of ADC nonlinearity in a mixed-signal compressive sensing system for frequency-domain sparse signals

Compressive sensing (CS) holds new promises for the digitization of wideband frequency-domain sparse signals at sub-Nyquist rate sampling without compromising the reconstruction quality. In this paper, the impact of ADC nonlinearity in a CS receiver for frequency-domain sparse signals is investigated. In a mixed-signal CS system, signals are randomized before sampling. The signal spectrum at each building block in the mixed-signal CS system is analyzed and compared to a conventional Nyquist-rate sampling system. It is shown that the signal randomization in a mixed-signal CS system is able to spread the spurious energy due to ADC nonlinearity along the signal bandwidth, rather than the concentration of harmonic distortion on a few frequencies as it is the case for a conventional ADC. As a result, this paper shows that a significant ADC SFDR (Spurious Free Dynamic Range) improvement is achieved in a CS receiver when processing sparse signals. Simulation results are reported which are in good agreement with the qualitative analysis.     

Electrical strength in ramp voltage AC tests of LDPE and its nanocomposites with silica and fibrous and laminar silicates

The electrical strength of a set of LDPE micro and nanocomposites with silica, laminar silicates and fibrous silicates has been studied. A significant 60% increase of the breakdown electrical field is shown by the microsized microdispersed LDPE/montmorillonite composites while only a 20% increase is obtained with a nanosized laminar silicate. Nanosized nanodispersed composites of the spherical silica and fibrous silicate with LDPE show a lower increase of the breakdown electrical field. The data point scatter in repeated tests is very high in the case of the microcomposites, indicating strong morphological heterogeneity, while it is very low in the nanocomposites. This implies that these nanocomposites are remarkably defect‐free as regards electrically “weak” sites. An analysis of the crystalline structure, semicrystalline morphology and inorganic particle size and distribution evidences the importance of the role played not only by the inorganic particles but also by the semicrystalline morphology in the final dielectric performance of the composite. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1301–1311, 2008     

Zur Kenntnis der Oxydation aromatischer und aliphatischer Ketoverbindungen mit Nitrobenzol in alkalischem Medium

Zusammenfassung Das in der Ligninchemie gebräuchlichste oxydative Abbauverfahren zu Vanillin, Syringaaldehyd etc. mittels Nitrobenzol und Alkali wurde auf Modellsubstanzen angewendet und näher studiert. Dabei zeigte sich, daß geeignete Oxoverbindungen zu Dioxoverbindungen oxydiert werden, welche unter den Versuchsbedingungen Benzilsäureumlagerungen (und eventuell auch intramolekulare Cannizzaro-Reaktionen) erleiden, wodurch Hydroxysäuren entstehen, die dann vielfach weiter zu Ketosäuren oxydiert werden können. Decarboxylierung liefert daraus Aldehyde wie z. B. Vanillin. Im Falle der Oxydation von Acetophenonderivaten bleibt die C-Sequenz erhalten, so daß das Oxydationsverfahren auch prinzipiell bei Arbeiten mit derartigen mit Radiokohlenstoff in der Seitenkette markierten Verbindungen anwendbar ist.Auch Verbindungen ohne Oxogruppen oder aktive Methylengruppen werden unter den Versuchsbedingungen oxydiert.Dem Präsidenten der Österr. Gesellschaft für Holzforschung. Herrn Direktor Dipl.-Ing.H. Lippert, zum 60. Geburtstag gewidmet.     

Multidimensional empirical quantiles: An application to the study of the weather in Brazil

This paper is the result of the practical need to specify local weather conditions that could help to design locally adapted telecommunication systems in Brazil. Several practical alternatives for defining multidimensional empirical quantiles are considered, as well as their possible applications, and the statistical problems involved.     

Solitary wave solutions to nonlinear evolution equations in mathematical physics

This paper obtains solitons as well as other solutions to a few nonlinear evolution equations that appear in various areas of mathematical physics. The two analytical integrators that are applied to extract solutions are tan–cot method and functional variable approaches. The soliton solutions can be used in the further study of shallow water waves in (1+1) as well as (2+1) dimensions.     

(N‐Heterocyclic carbene)Pd(triethylamine)Cl2 as precatalyst for the synthesis of Poly(triarylamine)s

The use of a highly active, air‐, and moisture‐stable N‐heterocyclic carbene‐palladium(II) complex for the polymerization of anilines and aryl dibromides or dichlorides by Buchwald‐Hartwig coupling is presented. In comparison to previous catalytic systems, higher molecular weight polymers with improved yields were obtained in shorter reaction times. The first examples of fabrication of OFETs with polytriarylamines synthesized with aryl dichlorides and anilines are also presented. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4904–4911     

Influence of microstructure and semi-crystalline morphology on the β and γ mechanical relaxations of the metallocene isotactic polypropylene

In this work, the characteristics of the β and γ mechanical relaxations, i.e., temperature and relative intensity, of a series of metallocene iPP samples (MPP) are analysed. The hypothesis that the temperature and the intensity of the glass transition (β relaxation) and local sub-T_g motions (γ relaxation) are related mainly to chain parameters and morphology has been corroborated. On the one hand, it has been found a critical average isotactic length (n₁) around 30 propylene units, under which the β and γ dynamics are promoted with respect to the α relaxation. On the other hand, it is apparent that the features which determine the degree of constraint within the inter-lamellar region, i.e., the fraction of low-T_m crystals, drive the relative intensities of the α, β and γ relaxation processes.