A number of materials have been explored for their use as artificial muscles Among these, dielectric elastomers (DEs) appear to provide the best combination of properties for true muscle-like actuation DEs behave as compliant capacitors, expanding in area and shrinking in thickness when a voltage is applied Materials combining very high energy densities, strains, and efficiencies have been known for some time To date, however, the widespread adoption of DEs has been hindered by premature breakdown and the requirement for high voltages and bulky support frames Recent advances seem poised to remove these restrictions and allow for the production of highly reliable, high-performance transducers for artificial muscle applications

Advances in dielectric elastomers for actuators and artificial muscles.

Dendron-mediated self-assembly, disassembly, and self-organization of complex systems have been investigated. The most ideal building blocks would need to display shape persistence in solution and in the solid state, since only this feature provides access to the use of complementary methods of structural analysis. Most supramolecular dendrimers are chiral even when they are constructed from nonchiral building blocks and are equipped with mechanisms that amplify chirality. This poses additional challenges associated with the understanding of the structural origin of chirality in different supramolecular structures through combinations of structural analysis methods. While many supramolecular structures assembled from dendrimers and dendrons resemble some of the related morphologies generated from block-copolymers, they are much more complex and are not determined by the volume ratio between the dissimilar parts of the molecule.

Dendron-Mediated Self-Assembly, Disassembly, and Self-Organization of Complex Systems

Altering the shape and properties of a material through external factors such as heat, light, pressure, pH, electric or magnetic fields, or the introduction of a guest molecule, is an attractive prospect. In this Perspective, piezochromic luminescent materials - which change the colour of their luminescence in response to mechanical stimuli - are described. Such piezochromism has been observed for a few molecular materials that contain luminescent cores in liquid-crystalline and crystalline solid states, as well as for polymeric materials doped with dyes. These changes in photoluminescent colour can be activated by various types of mechanical pressure such as shearing, grinding or elongation, which can trigger different mechanisms of producing the colour. Such stimuli-responsive materials have potential for various applications, including sensors, memory and displays.

Mechanically induced luminescence changes in molecular assemblies.

This review collects recent developments in the field of liquid crystalline elastomers (LCEs) with an emphasis on their use for actuator and sensor applications. Several synthetic pathways leading to crosslinked liquid crystalline polymers are discussed and how these materials can be oriented into liquid crystalline monodomains are described. By comparing the actuating properties of different systems, general structure-property relationships for LCEs are obtained. In the final section, how these materials can be turned into usable devices using different interdisciplinary techniques are described.

Liquid Crystalline Elastomers as Actuators and Sensors

A novel reagent for low-level detection in immunoadsorbent assays is described. The reagent consists of gold nanoparticles modified to integrate bioselective species (e.g., antibodies) with molecular labels for the generation of intense, biolyte-selective surface-enhanced Raman scattering (SERS) responses in immunoassays and other bioanalytical applications. The reagent is constructed by coating gold nanoparticles (30 nm) with a monolayer of an intrinsically strong Raman scatterer. These monolayer-level labels are bifunctional by design and contain disulfides for chemisorption to the nanoparticle surface and succinimides for coupling to the bioselective species. There are two important elements in this label design; it both minimizes the separation between label and particle surface and maximizes the number of labels on each particle. This approach to labeling also exploits several other advantages of SERS-based labels:  narrow spectral bandwidth, resistance to photobleaching and quenching, and long-wavel...

Femtomolar detection of prostate-specific antigen: an immunoassay based on surface-enhanced Raman scattering and immunogold labels.

Flow-induced phase transitions are a fundamental (but poorly understood) property of non-equilibrium systems, and are also of practical importance for tuning the processing conditions for plastics, petroleum products, and other related materials21. Recognition that polymers may exhibit liquid crystal properties has led to the discovery of the first tailored side-chain liquid crystal polymers (SCLCPs), which are formed by inserting a spacer between the main polymer chain and the lateral mesogen liquid–crystalline graftings22. Subsequent research has sought to understand the nature of the coupling between the main polymer chain and the mesogens, with a view to obtaining better control of the properties of these tailored structures22. We show here that the parallel or perpendicular orientation of the mesogens with respect to the main chain can be reversed by the application of an external field produced by a shear flow, demonstrating the existence of an isotropic nematic phase transition in SCLCPs. Such a transition, which was theoretically predicted1,2 for low-molecular-weight liquid crystals but never observed, is shown to be a general property of SCLCPs too. We expect that these SCLCPs will prove to be good candidate systems for the experimental study of these non-equilibrium phenomena.

Observation of shear-induced nematic-isotropic transition in side-chain liquid crystal polymers.

Two-component systems capable of self-assembling into soft gel-phase materials are of considerable interest due to their tunability and versatility. This paper investigates two-component gels based on a combination of a L-lysine-based dendron and a rigid diamine spacer (1,4-diaminobenzene or 1,4-diaminocyclohexane). The networked gelator was investigated using thermal measurements, circular dichroism, NMR spectroscopy and small angle neutron scattering (SANS) giving insight into the macroscopic properties, nanostructure and molecular-scale organisation. Surprisingly, all of these techniques confirmed that irrespective of the molar ratio of the components employed, the "solid-like" gel network always consisted of a 1:1 mixture of dendron/diamine. Additionally, the gel network was able to tolerate a significant excess of diamine in the "liquid-like" phase before being disrupted. In the light of this observation, we investigated the ability of the gel network structure to evolve from mixtures of different aromatic diamines present in excess. We found that these two-component gels assembled in a component-selective manner, with the dendron preferentially recognising 1,4-diaminobenzene (>70 %), when similar competitor diamines (1,2- and 1,3-diaminobenzene) are present. Furthermore, NMR relaxation measurements demonstrated that the gel based on 1,4-diaminobenzene was better able to form a selective ternary complex with pyrene than the gel based on 1,4-diaminocyclohexane, indicative of controlled and selective pi-pi interactions within a three-component assembly. As such, the results in this paper demonstrate how component selection processes in two-component gel systems can control hierarchical self-assembly.

Self-Assembly of Two-Component Gels: Stoichiometric Control and Component Selection

Backbone anisotropy and the structure of the mesophases of a series of side-chain liquid crystal polymers have been studied in the bulk by neutron scattering. The backbone conformation is obtained by small-angle neutron scattering on mixtures of hydrogenous polymers with deuteriated backbones. The components of the radius of gyration parallel, R ⊥ and perpendicular, R ∥ to the magnetic field are determined as a function of temperature for both the nematic phase and the smectic phase. It is shown that the polymer backbone is deformed in both phases. When the polymer exhibits only a nematic phase, it adopts a prolate conformation, where the average backbone direction is more or less parallel to the aligned mesogenic groups. Upon transition from the smectic phase to a nematic phase, the backbone in the nematic phase assumes a slightly oblate shape. This tendency towards oblate shape is due to the smectic fluctuations which are always present in such nematic phases. The exentricity of the oblate back...

On the structure and the chain conformation of side-chain liquid crystal polymers

Studies by small-angle neutron scattering have been conducted on a main-chain thermotropic nematic polymer composed of alternating mesogens and flexible spacers. The anisotropy of chain conformation in the nematic phase was measured in the melt and in a dilute nematic solution. The variation as a function of degree of polymerization and spacer length is discussed. The results agree favorably with a mean-field theory of wormlike chains.

Experimental evidence of chain extension at the transition temperature of a nematic polymer.

This article deals with the identification of solid-like properties measured at room temperature at a sub-millimetre length scale in liquid water. At a macroscopic scale, normal liquids (i.e. above melting temperature), and in particular water, are typically and empirically defined by the absence of shear elasticity, in contrast to solids or plastic fluids that require a stress threshold for flowing. A novel method optimizing the transmission of the shear stress to the sample enables a more complete probe of the mechanical response of liquids. It reveals that glass formers and viscous alkanes actually exhibit finite macroscopic shear elasticity away from any phase transition. This protocol is here applied for the first time to liquid water at room temperature, revealing, at the sub-millimetre scale, a low-frequency solid-like property.

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Laurence Noirez

Papers

Observation of shear-induced nematic-isotropic transition in side-chain liquid crystal polymers.

Self-Assembly of Two-Component Gels: Stoichiometric Control and Component Selection

On the structure and the chain conformation of side-chain liquid crystal polymers

Experimental evidence of chain extension at the transition temperature of a nematic polymer.

Identification of a low-frequency elastic behaviour in liquid water