Supramolecular concepts and new techniques in mechanochemistry: cocrystals, cages, rotaxanes, open metal-organic frameworks

Mechanochemical reactions effected by milling or grinding are an attractive means to conduct chemical reactions dependent on molecular recognition and to systematically explore different modes of molecular self-assembly. The natural relationship between milling mechanochemistry and supramolecular chemistry arises primarily from the ability to avoid bulk solvent, which simultaneously avoids limitations of solution-based chemistry, such as solubility, solvent complexation, or solvolysis, and makes the resulting process highly environmentally friendly. This tutorial review highlights the use of mechanochemistry for the synthesis of supramolecular targets in the solid state, such as molecular hydrogen- or halogen-bonded complexes, molecular and supramolecular cages, open frameworks and interlocked architectures. It is also demonstrated that the molecular self-assembly phenomena that are well-established in solution chemistry, such as reversible binding through covalent or non-covalent bonds, thermodynamic equilibration and structure templating, are also accessible in milling mechanochemistry through recently developed highly efficient methodologies such as liquid-assisted grinding (LAG) or ion- and liquid-assisted grinding (ILAG). Also highlighted are the new opportunities arising from the marriage of concepts of supramolecular and mechanochemical synthesis, including organocatalysis, deracemisation and discovery of new molecular recognition motifs.     

Seasonal changes of Rubisco content and activity in Fagus sylvatica and Picea abies affected by elevated CO2 concentration

We studied Rubisco (ribulose-1,5-bisphosphate carboxylase/oxygenase) content and activity in juvenile tree species ?? broadleaved Fagus sylvatica L. and coniferous Picea abies (L.) Karsten exposed for three growing seasons to ambient (A = 385 ??mol mol^?1) and elevated (E = 700 ??mol mol^?1) CO₂ concentrations. Rubisco content was determined by the SDS-PAGE method, Rubisco activity was assayed spectrophotometrically. The highest content of Rubisco enzyme in F. sylvatica was measured immediately after full leaf development followed by a gradual decrease throughout the growing season. By contrast, Rubisco content in P. abies increased markedly during the growing season. In both tree species, down-regulation of Rubisco content in trees cultivated under elevated CO₂ concentration was observed. Rubisco activity was stimulated in F. sylvatica by E treatment but not in P. abies. Because no significant differences were found in Rubisco activation state between A and E, we assume that stimulation of Rubisco activity in E is not a consequence of higher carbamylation but could be caused by the release of inhibitors from active sites of Rubisco under elevated CO₂.     

Dynamic stability of fcc crystals under isotropic loading from first principles

Lattice dynamics and stability of four fcc crystals (Al, Ir, Pt and Au) under isotropic (hydrostatic) tensile loading are studied from first principles using the linear response method and the harmonic approximation. The results reveal that, contrary to former expectations, strengths of all the studied crystals are limited by instabilities related to soft phonons with finite or vanishing wavevectors. The critical strains associated with such instabilities are remarkably lower than those related to the volumetric instability. On the other hand, the corresponding reduction of the tensile strength is by 20% at the most. An analysis of elastic stability conditions is also performed and the results obtained by means of both approaches are compared.     

The simulation of the origin and propagation of speckle field generated through a plane wave and Gaussian beam and its verification by speckle correlation method

This paper presents a simulation model of the origin and propagation of speckle field within the Fresnel approximation and verification of the model through a speckle correlation method for determination of in-plane object's translation. There is used a convolution form of the Fresnel–Kirchhoff diffraction integral in the simulation model instead of often used Fast Fourier Transform approach. A possible way of simulation of the light scattering by object's surface and in-plane translation of the illuminated surface is mentioned, whereas two types of illumination (plane wave and Gaussian beam) are used. Finally, results of numerical correlation of generated displaced speckle fields are shown and compared with the results obtained by theoretical relations.     

New probing techniques of radiative shocks

Radiative shock waves propagating in xenon at a low pressure have been produced using 60 joules of iodine laser (λ = 1.315 μm) at PALS center. The shocks have been probed by XUV imaging using a Zn X-raylaser (λ = 21 nm) generated with a 20-ns delay after the shock creating pulse. Auxiliary high-speed silicon diodes allowed performing space- and time-resolved measurement of plasma self-emission in the visible and XUV. The results show the generation of a shock wave propagating at 60 km/s preceded by a radiative precursor. This demonstrates the feasibility of radiative shock generation using high power infrared lasers and the use of XRL backlighting as a suitable diagnostic for shock imaging.     

Compact complex surfaces with geometric structures related to split quaternions

We study the problem of existence of geometric structures on compact complex surfaces that are related to split quaternions. These structures, called para-hypercomplex, para-hyperhermitian and para-hyperkähler, are analogs of the hypercomplex, hyperhermitian and hyperkähler structures in the definite case. We show that a compact 4-manifold carries a para-hyperkähler structure iff it has a metric of split signature together with two parallel, null, orthogonal, pointwise linearly independent vector fields. Every compact complex surface admitting a para-hyperhermitian structure has vanishing first Chern class and we show that, unlike the definite case, many of these surfaces carry infinite-dimensional families of such structures. We provide also compact examples of complex surfaces with para-hyperhermitian structures which are not locally conformally para-hyperkähler. Finally, we discuss the problem of non-existence of para-hyperhermitian structures on Inoue surfaces of type S⁰$S^0$ and provide a list of compact complex surfaces which could carry para-hypercomplex structures.     

Quasi-particle fermionic formulas for (k, 3)-admissible configurations

We construct new monomial quasi-particle bases of Feigin-Stoyanovsky type subspaces for the affine Lie algebra sl(3;ℂ)∧ from which the known fermionic-type formulas for (k, 3)-admissible configurations follow naturally. In the proof we use vertex operator algebra relations for standard modules and coefficients of intertwining operators.     

Properties of rubber filled with montmorillonite with various surface modifications

Layered silicate/natural rubber composites were prepared by direct polymer melt intercalation. Na‐montmorillonite Kunipia‐F and its organic derivates (organo‐clays) prepared by ion exchange were used as clay fillers. Silica (SiO₂) Ultrasil VN3, a filler commonly used in the rubber industry, was used in combination with clay fillers. The effect of clay or organo‐clay loading from 1 up to 10 phr without (0 phr) or with silica (15 phr) showed significant improvement of the tensile properties (stress at break, strain at break and modulus M100). Modification of montmorillonite by three alkylammonium cations with the same length of alkylammonium chain (18 carbons) and different structure resulted in altered reinforcing and plasticizing effects of the filler in composites with rubber matrix. Copyright © 2011 John Wiley & Sons, Ltd.     

Electron paramagnetic resonance line shifts and line shape changes due to heisenberg spin exchange and dipole-dipole interactions of nitroxide free radicals in liquids 8. Further experimental and theoretical efforts to separate the effects of the two interactions

The work in part 6 of this series (J. Phys. Chem. A 2009, 113, 4930), addressing the task of separating the effects of Heisenberg spin exchange (HSE) and dipole-dipole interactions (DD) on electron paramagnetic resonance (EPR) spectra of nitroxide spin probes in solution, is extended experimentally and theoretically. Comprehensive measurements of perdeuterated 2,2,6,6-tetramethyl-4-oxopiperidine-1-oxyl (pDT) in squalane, a viscous alkane, paying special attention to lower temperatures and lower concentrations, were carried out in an attempt to focus on DD, the lesser understood of the two interactions. Theoretically, the analysis has been extended to include the recent comprehensive treatment by Salikhov (Appl. Magn. Reson. 2010, 38, 237). In dilute solutions, both interactions (1) introduce a dispersion component, (2) broaden the lines, and (3) shift the lines. DD introduces a dispersion component proportional to the concentration and of opposite sign to that of HSE. Equations relating the EPR spectral parameters to the rate constants due to HSE and DD have been derived. By employing nonlinear least-squares fitting of theoretical spectra to a simple analytical function and the proposed equations, the contributions of the two interactions to items 1-3 may be quantified and compared with the same parameters obtained by fitting experimental spectra. This comparison supports the theory in its broad predictions; however, at low temperatures, the DD contribution to the experimental dispersion amplitude does not increase linearly with concentration. We are unable to deduce whether this discrepancy is due to inadequate analysis of the experimental data or an incomplete theory. A new key aspect of the more comprehensive theory is that there is enough information in the experimental spectra to find items 1-3 due to both interactions; however, in principle, appeal must be made to a model of molecular diffusion to separate the two. The permanent diffusion model is used to illustrate the separation in this work. In practice, because the effects of DD are dominated by HSE, negligible error is incurred by using the model-independent extreme DD limit of the spectral density functions, which means that DD and HSE may be separated without appealing to a particular model.     

Desymmetrisation of aromatic diamines and synthesis of non-symmetrical thiourea derivatives by click-mechanochemistry

ortho- and para-Phenylenediamines were desymmetrised and quantitatively transformed into mono- and bis-(thio)ureas or mixed thiourea-ureas through a one-pot mechanochemical click reaction sequence; mechanochemical desymmetrisation proceeds quantitatively without excess reagents and allows the controlled extension of a molecular structure by combining normally competing reactions.