A Multi‐Addressable Switch Based on the Dimethyldihydropyrene Photochrome with Remarkable Proton‐Triggered Photo‐opening Efficiency

A series of photochromic derivatives based on the trans‐10b,10c‐dimethyl‐10b,10c‐dihydropyrene (DHP, “closed form”) skeleton has been synthesized and their photoisomerization leading to the corresponding cyclophanediene (CPD, “open form”) isomers has been investigated by UV/Vis and ¹H NMR spectroscopies. Substitution of the DHP core with electron‐withdrawing pyridinium groups was found to have major effects on the photoisomerization efficiency, the most remarkable examples being to enhance the quantum yield of the opening reaction and to allow fast and quantitative conversions at much lower radiant energies. This effect was rationalized by theoretical calculations. We also show that the reverse reaction, that is, going from the open form to the closed form, can be electrochemically triggered by oxidation of the CPD unit and that the photo‐opening properties of pyridine‐substituted DHPs can be efficiently tuned by protonation, the system behaving as a multi‐addressable molecular switch. These multi‐addressable photochromes show promise for the development of responsive materials.     

Polyaniline/montmorillonite nanocomposite thin layers deposited on different substrates

Preparation method of polyaniline/montmorillonite (PANI/MMT) nanocomposite in the form of thin layer deposited on various substrates is optimized in this work to obtain high electrical conductivity. Simple method (i.e. polymerization of anilinium sulfate in the presence of MMT) has been used for the preparation and following four conditions were varied: preparation temperature (T = 10 or 20 °C), preparation time (t = 4 or 6 h), size fraction of MMT (p < 1 or 5 µm), and type of substrate (microscope glass slides, silica glass slides, polyester foils). Therefore, 24 samples were prepared, characterized and their electrical conductivity was compared. Raman spectroscopy and scanning electron microscopy were used for the characterization of the structure of samples. Thickness of layers was measured using atomic force microscopy. Based on the comparison of samples and with respect to the aim of obtaining high electrical conductivity, it was found that the most suitable substrate is polyester foil and preparation conditions are T = 20 °C, t = 6 h, p < 5 µm. To obtain highly conductive layers on glass substrates (although less conductive than layers on foil), preparation time have to be shortened to 4 h.     

Solvent-free silica gel mediated decarboxylation of C–O coupling products of β-diketones and β-oxo esters with malonyl peroxides

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Towards Polyoxometalate‐Cluster‐Based Nano‐Electronics

We explore the concept that the incorporation of polyoxometalates (POMs) into complementary metal oxide semiconductor (CMOS) technologies could offer a fundamentally better way to design and engineer new types of data storage devices, due to the enhanced electronic complementarity with SiO₂, high redox potentials, and multiple redox states accessible to polyoxometalate clusters. To explore this we constructed a custom‐built simulation domain bridge. Connecting DFT, for the quantum mechanical modelling part, and mesoscopic device modelling, confirms the theoretical basis for the proposed advantages of POMs in non‐volatile molecular memories (NVMM) or flash‐RAM.     

Application of diffusion‐edited NMR spectroscopy for selective suppression of water signal in the determination of monomer composition in alginates

Alginate is a linear copolymer of 1‐4 linked β‐D ‐mannuronic acid (M) and 1‐4 linked α‐L ‐guluronic acid (G). The physical properties of these polysaccharides such as gel properties and viscosity are largely correlated to the monomer composition (M/G ratio), the sequence of the polymer and the molecular weight. Determination of the M/G ratio is therefore important and NMR spectroscopy is among the most common methods used to accurately obtain this ratio. Instead of using time consuming, possibly sample altering, acid hydrolysis to reduce the viscosity of the alginate sample prior to analysis, samples of low concentrations can be used. However, this results in a water peak in the NMR spectrum that is several orders of magnitude larger than the alginate signals and water suppression is required. In this article, a diffusion‐edited NMR experiment that suppresses the water peak while retaining the signals of interest has been used to enable correct M/G ratio determination. This approach exploits the difference in translational diffusion between the larger alginate molecules and the smaller water molecules. Using this method, the monomer composition of 20 different alginate powders was determined. The diffusion parameters were optimized to allow measurement for samples covering a large range of M/G ratios and viscosities. Thus, such method should be useful for analyzing large numbers of unknown alginate samples using, for example, automation procedures. Copyright © 2011 John Wiley & Sons, Ltd.     

Stability of the rectilinear motion of a railway Wheelset

A railway wheelset rolling on rails without slip is studied with consideration of the creep hypothesis. The wheelset is represented by two cones having a common base; the rails are represented by two circular cylinders with parallel axes. The kinematic characteristics of undisturbed rolling for the wheelset are determined when its center of mass moves along a straight line; these characteristics are also determined in the case of disturbed motion when the mass center of the wheelset moves along a sinusoidal trajectory. For these modes of motion, the constraint reactions are found with an accuracy up to the second order of smallness with respect to the values of disturbed variables. When the absolutely rigid point contact is replaced by the elastic contact, the creep hypothesis is used, the method of averaging with respect to the fast variables is applied, and a critical velocity above which the rectilinear rolling becomes unstable is determined on the basis of the averaged equations.     

Temperature field formation in a planet due to tidal deformations

A model of a planet considered as a homogeneous viscoelastic sphere in the gravitational field of a point mass is discussed. Tidal deformations occur in the process of their mutual motion. The deformation rate tensor and the corresponding dissipative function are found. The time variation of the deformation tensor components accompanied by the heat release at each point of the planet causes the formation of a temperature field described by the inhomogeneous heat conduction equation. The temperature field is determined by averaging with respect to the proper rotation angle and is estimated for the Moon.     

Cathodoluminescence of iodine dimers in KCl:I crystals

Radiative characteristics of localized exciton states in a KCl:I crystal have been studied in the temperature range 27–200 K by pulsed optical spectroscopy with nanosecond-range time resolution. Besides the bands investigated earlier in KCl:I crystals at impurity concentrations above 0.1 mol %, a strong band peaked at 3.8 eV was detected. The temperature dependences of the decay times, amplitude values of the intensity, and light sums of the 3.8-and 3.4-eV bands were studied. These bands are shown to originate from radiative decay of localized excitons bound to the impurity dimers.