Observation of the ordered growth of coronene on Ag(111): a scanning tunnelling microscopy study of vacuum deposited molecules

The molecular ordering of coronene (C24H12) obtained by vacuum-deposition onto predominantly Ag(111) on mica has been investigated using the scanning tunnelling microscope. Real-space topographic images reveal that in certain regions we obtain layer-by-layer ordered growth of the molecules on this substrate which agrees with previous indirect measurements (the growth did not display this ordering in other regions). In our experiments on the ordered regions, we observe the best imaging contrast at a voltage bias of -0.28 V which may correspond to a resonant tunnelling process through the molecules. © 1995.

Spontaneous formation of highly ordered nanostructures: thermal instability and mode selection in surface-capped polymer films.

We demonstrate a controllable formation process of wave-like patterns in thermally unstable surface-capped polymer films on a rigid substrate. Self-ordered wave-like structures over a large area can be created by applying a small lateral tension to the film, whereupon it becomes unstable. A clear mode selection process which includes creation, decay and interference between coexisting waves at different annealing conditions has been observed, which makes it possible to restrain the patterns which are formed finally. Our results provide a clear and new evidence of spinodal behaviour in such a film due to thermal instability. Furthermore, we show that the well-controlled patterns generated in such a process can be used to fabricate nanostructures for various applications.

Population of nonnative states of lysozyme variants drives amyloid fibril formation.

The propensity of protein molecules to self-assemble into highly ordered, fibrillar aggregates lies at the heart of understanding many disorders ranging from Alzheimer's disease to systemic lysozyme amyloidosis. In this paper we use highly accurate kinetic measurements of amyloid fibril growth in combination with spectroscopic tools to quantify the effect of modifications in solution conditions and in the amino acid sequence of human lysozyme on its propensity to form amyloid fibrils under acidic conditions. We elucidate and quantify the correlation between the rate of amyloid growth and the population of nonnative states, and we show that changes in amyloidogenicity are almost entirely due to alterations in the stability of the native state, while other regions of the global free-energy surface remain largely unmodified. These results provide insight into the complex dynamics of a macromolecule on a multidimensional energy landscape and point the way for a better understanding of amyloid diseases.

Controlling magnetic ordering in coupled nanomagnet arrays

We have fabricated using high-resolution electron beam lithography circular magnetic particles (nanomagnets) of diameter 60 nm and thickness 7 nm out of the common magnetic alloy supermalloy. The nanomagnets were arranged on rectangular lattices of different periods. A high-sensitivity magneto-optical method was used to measure the magnetic properties of each lattice. We show experimentally how the magnetic properties of a lattice of nanomagnets can be profoundly changed by the magnetostatic interactions between nanomagnets within the lattice. We find that simply reducing the lattice spacing in one direction from 180 nm down to 80 nm (leaving a gap of only 20 nm between edges) causes the lattice to change from a magnetically disordered state to an ordered state. The change in state is accompanied by a peak in the magnetic susceptibility. We show that this is analogous to the paramagnetic-ferromagnetic phase transition which occurs in conventional magnetic materials, although low-dimensionality and kinetic effects must also be considered.

Measurement of forces during the modification of C60 islands

A UHV atomic force microscope with a conducting tip is used to measure the tip-sample conductance as a function of the applied force on well-ordered, monolayer islands of C60 on Cu(111). By imaging the sample before and after each force-distance experiment, it was possible to investigate the forces required for the removal of individual C60 molecules from the islands. The removal of C60 occurs near defects or edges of the C60 islands and requires an applied force of 5-20 nN, which corresponds to applied pressures of order 1 GPa. In addition, it was possible to investigate the strength of the C60 film on the molecular scale. It was found that the mechanical stiffness of a C60 molecule is of order 6 N/m and the islands appear to undergo a reversible yield process at an applied pressure of around 1.2 GPa.

Ferroelectric liquid crystal mixtures containing chiral ether and ester compounds with the 2-arylidene-p-menthan-3-one skeleton

Some 1R,4R-2-(4-phenylbenzylidene)-p-menthane-3-one derivatives containing the ether or ester linking group between benzene rings of the arylidene fragment have been studied as chiral dopants in ferroelectric liquid crystal systems based on the eutectic mixture (1:1) of two phenylbenzoate derivatives CmH2m+1OC6H4COOC6 H4OCnH2n+1 (n = 6; m = 8, 10). The ferroelectric properties of these compositions (spontaneous polarization, rotation viscosity, smectic tilt angle as well as quantitative characteristics of their concentration dependences) were compared with those for systems including chiral dopants containing no linking group. Ferroelectric parameters of the induced ferroelectric compositions studied have been shown to depend essentially on the presence of the linking group between benzene rings and its nature as well as on the number of the benzene rings in the rigid molecular core of the chiral dopants used. For all ferroelectric liquid crystal systems studied, the influence of the chiral dopants on the thermal stability of N*, SmA and SmC* mesophases has been quantified. The influence of the linking group nature in the dopant molecules on the characteristics of the systems studied is discussed taking into account results of the conformational analysis carried out by the semi-empirical AM1 and PM3 methods.

New chiral mesogens 3(R)-methylcyclohexanone derivatives

New chiral compounds 3R-methylcyclohexanone derivatives were synthesized. These compounds were revealed to exhibit the mesomorphic behavior within rather wide temperature ranges. Types of formed mesophases and phase transition temperatures were determined by polarizing microscopy, differential scanning calorimetry and small angle scattering of X-ray. Mesomorphic properties of the new chiral compounds were compared with those for the chiral 2-arylidene derivatives of 3R,6R-3-methyl-6-isopropylcyclohexanone (d-isomenthone) studied earlier. Distinctions between these two types of compounds in an ability to form mesophases and also in twisting properties as chiral dopants in induced cholesteric mesophases are considered.

Photonics and lasing in liquid crystal materials

Owing to fundamental reasons of symmetry, liquid crystals are soft materials. This softness allows long length-scales, large susceptibilities and the existence of modulated phases, which respond readily to external fields. Liquid crystals with such phases are tunable, self-assembled, photonic band gap materials; they offer exciting opportunities both in basic science and in technology. Since the density of photon states is suppressed in the stop band and is enhanced at the band edges, these materials may be used as switchable filters or as mirrorless lasers. Disordered periodic liquid crystal structures can show random lasing. We highlight recent advances in this rapidly growing area, and discuss future prospects in emerging liquid crystal materials. Liquid crystal elastomers and orientationally ordered nanoparticle assemblies are of particular interest. © 2006 The Royal Society.

New (1R,4R)-2-arylidene-p-menthan-3-ones with a bridging ester group in the arylidene fragment. Synthesis and behavior in liquid-crystalline systems

(1R,4R)-2-(4-Hydroxybenzylidene)- and (1R,4R)-2-(4′-hydroxybiphenyl- 4-yl)methylene-p-menthan-3-ones were synthesized by condensation of (-)-menthone with O-tetrahydropyran-2-yl derivatives of 4-hydroxybenzaldehyde and 4′-hydroxy-4-formylbiphenyl, respectively, in a DMSO - base medium followed by the removal of the protective group. The reactions of these hydroxy derivatives with 4-alkylbenzoic, 4-alkyloxybenzoic, trans-4-alkylcyclohexane-4- carboxylic, and 4′-alkylbiphenyl-4-carboxylic acids afforded three series of new chiral esters. Compounds containing the arylidene moiety with three benzene rings were found to exhibit liquid-crystalline properties. The characteristic features of these compounds are discussed based on the results of studies by polarizing microscopy, differential scanning calorimetry, and small-angle X-ray scattering. It was found that the mesomorphic compounds under study can form a smectic A mesophase, twist grain boundary mesophases (TGBA), and blue phases in a wide temperature range. Upon dissolution of certain of chiral compounds in 4′-cyano-4-pentylbiphenyl, a rather high twisting power and the thermal stabilizing effect on mesophases were observed.

Perylene-based fluorescent liquid crystal dye guest-host mixtures

We present a study on a series of dye guest-host mixtures using fluorescent perylene-based molecules as the guest dye in an organosiloxane host. These hosts have temperature-independent switching, at room temperature, through 90° for fields of the order of 10 Vrms/μm. Perylene molecules have been grafted onto the organosiloxane moiety via an alkyl spacer producing novel and rugged fluorescent dyes that are readily miscible in the host. Micro-separation of the low molar mass siloxane groups in the mesophases tend to form smectic phases. These planes produce an effective two-dimensional polymer backbonethat engenders the rugged mechanical properties of polymeric liquid crystals onto these low molar mass ferroelectric liquid crystals. In this study we show how the introduction of the dye molecules affects the electro-optic properties of the organosiloxane host. © 2001 OPA (Overseas Publishers Association) N.V. Published by license under the Gordon and Breach Science Publishers imprint, a member of the Taylor & Francis Group,.

Biomimetic layer-by-layer assembly of artificial nacre.

Nacre is a technologically remarkable organic-inorganic composite biomaterial. It consists of an ordered multilayer structure of crystalline calcium carbonate platelets separated by porous organic layers. This microstructure exhibits both optical iridescence and mechanical toughness, which transcend those of its constituent components. Replication of nacre is essential for understanding this complex biomineral, and paves the way for tough coatings fabricated from cheap abundant materials. Fabricating a calcitic nacre imitation with biologically similar optical and mechanical properties will likely require following all steps taken in biogenic nacre synthesis. Here we present a route to artificial nacre that mimics the natural layer-by-layer approach to fabricate a hierarchical crystalline multilayer material. Its structure-function relationship was confirmed by nacre-like mechanical properties and striking optical iridescence. Our biomimetic route uses the interplay of polymer-mediated mineral growth, combined with layer-by-layer deposition of porous organic films. This is the first successful attempt to replicate nacre, using CaCO(3).