The Story Behind the Link between Molecular Chirality and Crystal Shape

Here we describe the story behind the link between molecular chirality and macroscopic phenomena, the latter being a probe for the direct assignment of absolute configuration of chiral molecules. First, a brief tour of the history of molecular stereochemistry, starting with the classic experiment reported by Pasteur in 1848 on the separation of enantiomorphous crystals of a salt of tartaric acid, and his conclusion that the molecules of life are chiral of single-handedness. With time, this study raised, inter alia, two fundamental questions: the absolute configuration of chiral molecules and how a molecule of given configuration shapes the enantiomorphous morphology of its crystal. As for the first question, following the beginning of crystal structure determination by X-ray diffraction in 1912, it took almost 40 years before Bijvoet assigned molecular chirality through the esoteric method involving anomalous X-ray scattering. We have been able to address and link both questions through ‘everyday concepts of left and right’ (in the words of Jack Dunitz) by the use of ‘tailor-made’ auxiliaries. By such means, it proved possible to reveal, through morphology, etch patterns, epitaxy and symmetry reduction of both chiral and, paradoxically, centrosymmetric crystals, the basic chiral symmetry of the molecules of life, the α-amino acids and sugars.     

Analysis of viscoelastic contact with normal compliance,friction and wear diffusionAnalyse d'un problème viscoélastique avec compliance normale,frottement et diffusion d'usure

We consider a quasistatic problem of frictional contact between a viscoelastic body and a moving foundation. The contact is with wear and is modeled by normal compliance and a law of dry friction. The novelty in the model is that it allows for the diffusion of the wear debris over the potential contact surface. Such kind of phenomena arise in orthopaedic biomechanics and influence the properties of joint prosthesis. We derive a weak formulation of the problem and state that, under a smallness assumption on the problem data, there exists a unique weak solution for the model. To cite this article: M. Shillor et al., C. R. Mecanique 331 (2003).     

Many symmetrically indivisible structures

A structure in a first‐order language is indivisible if for every colouring of its universe M in two colours, there is a monochromatic such that . Additionally, we say that is symmetrically indivisible if can be chosen to be symmetrically embedded in (that is, every automorphism of can be extended to an automorphism of ). In the following paper we give a general method for constructing new symmetrically indivisible structures out of existing ones. Using this method, we construct many non‐isomorphic symmetrically indivisible countable structures in given (elementary) classes and answer negatively the following question from 6 : Let be a symmetrically indivisible structure in a language . Let . Is symmetrically indivisible?     

Electronic transport in graphene nanostructures on SiO2

We report two experiments on graphene nanostructures. The first was performed on a graphene nanoribbon, where the nature of electronic transport was investigated in detail. Electrons or holes are found to localize in pockets of the potential along the ribbon. Transport is governed by the joint action of localization and Coulomb interaction. The temperature-dependence of the conductance shows activated behavior at temperatures above a few Kelvin. The activation energy retraces the edges of Coulomb blockade diamonds found in nonlinear transport. In the second experiment the metallic tip of a low-temperature scanning force microscope was scanned above a graphene quantum dot. In addition to the familiar Coulomb blockade fringes, localized states are detected forming in the constrictions connecting the dot to source and drain.     

Heterogeneous Electrofreezing of Super-Cooled Water on Surfaces of Pyroelectric Crystals is Triggered by Trigonal Planar Ions

Electrofreezing experiments of super-cooled water (SCW) with different ions, performed directly on the charged hemihedral faces of pyroelectric LiTaO₃ and AgI crystals, in the presence and in the absence of pyroelectric charge are reported. It is demonstrated that bicarbonate (HCO₃⁻) ions elevate the icing temperature near the positively charged faces. In contrast, the hydronium (H₃O⁺) slightly reduces the icing temperature. Molecular dynamics simulations suggest that the hydrated trigonal planar HCO₃⁻ ions self-assemble with water molecules near the surface of the AgI crystal as clusters of slightly different configuration from those of the ice-like hexagons. These clusters, however, have a tendency to serve as embryonic nuclei for ice crystallization. Consequently, we predicted and experimentally confirmed that the trigonal planar ions of NO₃⁻ and guanidinium (Gdm⁺), at appropriate concentrations, elevate the icing temperature near the positive and negative charged surfaces, respectively. On the other hand, the Cl⁻ and SO₄²⁻ ions of different configurations reduce the icing temperature.     

Bifunctional Nanoscale Assemblies: Multistate Electrochromics Coupled with Charge Trapping and Release

We demonstrate controlled charge trapping and release, accompanied by multiple color changes in a metallo‐organic bilayer. The dual functionality of the metallo‐organic materials provides fundamental insight into the metal‐mediated electron transport pathways. The electrochemical processes are visualized by distinct, four color‐to‐color transitions: red, transparent, orange, and brown. The bilayer is composed of two elements: 1) a nanoscale gate consisting of a layer of well‐defined polypyridyl ruthenium complexes bound to a flexible transparent electrode, and 2) a charge storage layer consisting of isostructural iron complexes attached to the surface of the gate. This gate mediates or blocks electron transport in response to an applied voltage. The charge storage and release depend on the oxidation state of the layer of ruthenium complexes (=gate). Combining electrochemistry with optical data revealed mechanistic information: the brown coloration of the bilayer directly relates to the formation of intermediate ruthenium species, providing evidence for catalytic positive charge release mediated through the gate.     

Thermal Intercalation of Alkali Halides into Kaolinite

Solid state intercalation of alkali halides into kaolinite takes place by heating pressed disks of dimethylsulfoxide (DMSO)-kaolinite complex ground in different alkali halides. This reaction involves diffusion of the DMSO outside the interlayer space and the alkali halide into the interlayer space. IR and Raman spectroscopy reveal two types of intercalation complexes: (i) almost non-hydrous, obtained during thermal treatment of the DMSO complex; and (ii) hydrated, obtained by regrinding the disk in air. The strength of the hydrogen bonds between intercalated water or halide anions and the inner surface hydroxyls decreases in the order Cl⁻>Br⁻>I⁻. Chlorides penetrate the ditrigonal holes and form hydrogen bonds with the inner OH groups. This revised version was published online in August 2006 with corrections to the Cover Date.     

Steady flow in a deformable porous medium

A nonlinear model for a steady flow in a deformable porous medium is considered. The flow is governed by the poroelasticity system consisting of an elasticity equation for the displacement of the porous medium and Darcy's equation for the pressure in the fluid. This poroelasticity system is nonlinear when the permeability in Darcy's equation is assumed to depend on the dilatation of the porous medium. Existence and uniqueness of a weak solution of this poroelasticity system is established under rather weak assumptions on the regularity of the data. Convergence of a finite element approximation is proved and verified through numerical experiments. Copyright © 2013 John Wiley & Sons, Ltd.     

Processes with no standard extension

Using an example of A. Vershik, a class of processes is introduced with the property that they do not admit astandard extension. This provides a simple proof that Vershik's example process does not admit a standard extension. Supported in part by The Israel Science Foundation.