Volume confinement induced microstructural transitions and property enhancements of supramolecular soft materials

The rheological properties of supramolecular soft functional materials are determined by the networks within the materials. This research reveals for the first time that the volume confinement during the formation of supramolecular soft functional materials will exert a significant impact on the rheological properties of the materials. A class of small molecular organogels formed by the gelation of N-lauroyl-L-glutamic acid din-butylamide (GP-1) in ethylene glycol (EG) and propylene glycol (PG) solutions were adopted as model systems for this study. It follows that within a confined space, the elasticity of the gel can be enhanced more than 15 times compared with those under un-restricted conditions. According to our optical microscopy observations and rheological measurements, this drastic enhancement is caused by the structural transition from a multi-domain network system to a single network system once the average size of the fiber network of a given material reaches the lowest dimension of the system. The understanding acquired from this work will provide a novel strategy to manipulate the network structure of soft materials, and exert a direct impact on the micro-engineering of such supramolecular materials in micro and nano scales.

Critical behavior of confined supramolecular soft materials on a microscopic scale

The formation of fiber networks and the resulting rheological properties of supramolecular soft materials are dramatically influenced when the volume of the system is reduced to a threshold. Unlike un-confined systems, the formation of fiber networks under volume confinement is independent of temperature and solute concentration.

Microengineering of supramolecular soft materials by design of the crystalline fiber networks

Crystalline spherulitic fiber networks are commonly observed in polymeric and supramolecular functional materials. The elasticity of materials with this type of network is low if interactions between the individual spherulites are weak (mutually exclusive). Improving the elasticity of these materials is necessary because of their important applications in many fields. In this work, the engineering of the microstructures and rheological properties of this type of material is carried out. A small molecule organogel formed by the gelation of N-lauroyl-L-glutamic acid di-n-butylamide (GP-1) in propylene glycol (PG) is used as an example. The elasticity of this material is improved by controlling the thermodynamic driving force, the supersaturation of the gelator, and by using a selected copolymer additive to manipulate the primary nucleation of GP-1. Because of the weak interactions between the GP-1 spherulites, with the same fiber mass, the elasticity of GP-1/PG gel is less than half of those of the other two gels formed by GP-1 and 2-hydroxystearlic acid in solvent benzyl benzoate (BB), which are supported by interconnecting spherulitic fiber networks. This work develops a robust approach to the engineering of supramolecular functional materials especially those with mutually exclusive spherulite fiber networks.

Controlling nanoparticle formation via sizable cages of supramolecular soft materials

We present a new generic strategy to fabricate nanoparticles in the “cages” within the fibrous networks of supramolecular soft materials. As the cages can be acquired by a design-and-production manner, the size of nanoparticles synthesized within the cages can be tuned accordingly. To implement this idea, both selenium and silver were chosen for the detailed investigation. It follows that the sizes of selenium and silver nanoparticles can be controlled by tuning the pore size of the fiber networks in the material. When the concentration of the gelator is high enough, monodisperse nanoparticles can be prepared. More interestingly, the morphology of the nanoparticles can be altered: silver disks can be formed when the concentrations of both the gelator and silver nitrate are sufficiently low. As the fiber network serves as a physical barrier and semisolid support for the nanoparticles, the stability in the aqueous media and the ease of application of these nanoparticles can be substantially enhanced. This robust surfactant-free approach will not only allow the controlled fabrication of nanoparticles, but also can be applied to the fabrication of composite materials for robust applications.

Size invariance of fibrous networks of supramolecular soft materials during formation under critical volume confinement

The rheological properties of a hierarchically structured supramolecular soft material are mainly determined by the structure of its network. Controlling the thermodynamic driving force of physical gels (one type of such materials) during the formation has proven effective in manipulating the network structure due to the nature of nucleation and growth of the fiber network formation in such a supramolecular soft material. Nevertheless, it is shown in this study that such a property can be dramatically influenced when the volume of the system is reduced to below a threshold value. Unlike un-confined systems, the network structure of such a soft material formed under volume confinement contains a constant network size, independent of the experimental conditions, i.e. temperature and solute concentration. This implies that the size of the fiber networks in such a material is invariable and free from the influence of external factors, once the volume is reduced to a threshold. The observations of this work are significant in the control of the formation of fibrous networks in materials of this type.

Control of crystallization in supramolecular soft materials engineering

As one class of the most important supramolecular functional materials, gels formed by low molecular weight gelators (LMWGs) have many important applications. The key important parameters affecting the in-use performance of a gel are determined by the hierarchical fiber network structures. Fiber networks consisting of weakly interacting multiple domains are commonly observed in gels formed by LMWGs. The rheological properties, particularly the elasticity, of a gel with such a fiber network are weak due to the weak interactions between the individual domains. As achieving desirable rheological properties of such a gel is practically relevant, in this work, we demonstrate the engineering of gels with such a type of fiber network by controlling crystallization of the gelator. Two example gels formed by a glutamic acid derivative in a non-ionic surfactant Tween 80 and in propylene glycol were engineered by controlling the thermodynamic driving force for crystallization. For a fixed gelator concentration, the thermodynamic driving force was manipulated by controlling the temperature for fiber crystallization. It was observed that there exists an optimal temperature at which a gel with maximal elasticity can be fabricated. This will hopefully provide guidelines for producing high performance soft materials by engineering their fiber network structures.

Architecture of supramolecular soft functional materials: from understanding to micro-/nanoscale engineering

This article gives an overview of the current progress of a class of supramolecular soft materials consisting of fiber networks and the trapped liquid. After discussing the up-to-date knowledge on the types of fiber networks and the correlation to the rheological properties, the gelation mechanism turns out to be one of the key subjects for this review. In this concern, the following two aspects will be focused upon: the single fiber network formation and the multi-domain fiber network formation of this type of material. Concerning the fiber network formation, taking place via nucleation, and the nucleation-mediated growth and branching mechanism, the theoretical basis of crystallographic mismatch nucleation that governs fiber branching and formation of three-dimensional fiber networks is presented. In connection to the multi-domain fiber network formation, which is governed by the primary nucleation and the subsequent formation of single fiber networks from nucleation centers, the control of the primary nucleation rate will be considered. Based on the understanding on the the gelation mechanism, the engineering strategies of soft functional materials of this type will be systematically discussed. These include the control of the nucleation and branching-controlled fiber network formation in terms of tuning the thermodynamic driving force of the gelling system and introducing suitable additives, as well as introducing ultrasound. Finally, a summary and the outlook of future research on the basis of the nucleation-growth-controlled fiber network formation are given.

Multi-component, Self-assembled, Functional Soft Materials

Supramolecular chemistry is an emerging tool for devising materials that can perform specified functions. The self-assembly of facially amphiphilic bile acid molecules has been extensively utilized for the development of functional soft materials. Supramolecular hydrogels derived from the bile acid backbone act as useful templates for the intercalation of multiple components. Based on this, synthesis of gel-nanoparticle hybrid materials, photoluminescent coating materials, development of a new enzyme assay technique, etc. were achieved in the author's laboratory. The present account highlights some of these achievements.

Tribological response of soft materials sliding against hard surface textures at various numbers of cycles

In the present investigation, various kinds of textures were attained on the steel surfaces. Roughness of the textures was varied using different grits of emery papers or polishing powders. Pins made of pure Al, Al-4Mg alloy and pure Mg were then slid against prepared steel plate surfaces at various numbers of cycles using an inclined pin-on-plate sliding tester. Tests were conducted at a sliding velocity of 2mms(-1) in ambient conditions under both dry and lubricated conditions. Normal loads were increased up to 110N during the tests. The morphologies of the worn surfaces of the pins and the formation of transfer layer on the counter surfaces were observed using a scanning electron microscope. Surface roughness parameters of the plate were measured using an optical profilometer. In the experiments, it was observed that the coefficient of friction and formation of a transfer layer (under dry and lubricated conditions) only depended on surface texture during the first few sliding cycles. The steady-state variation in the coefficient of friction under both dry and lubrication conditions was attributed to the self-organisation of texture of the surfaces at the interface during sliding. Copyright (C) 2012 John Wiley & Sons, Ltd.

White light emitting soft materials from off-the-shelf ingredients

Balanced white light emitting systems are important for applications in electronic devices. Of all types of white light emitting materials, gels have the special advantage of easy processability. Here we report two white light emitting gels, which are based on lanthanide cholate self-assembly. The components are commercially available and the gels are prepared by simply sonicating their aqueous solutions (1-3min), unlike any other known white light emitting systems. Their CIE co-ordinates, calculated from the luminescence data, fall in the white light range with a correlated color temperature of ca. 5600 K.

SupraMOFs: Supramolecular porous materials assembled from metal-nucleobase discrete entities

289 p.

Cognition from the bottom up: on biological inspiration, body morphology, and soft materials.

Traditionally, in cognitive science the emphasis is on studying cognition from a computational point of view. Studies in biologically inspired robotics and embodied intelligence, however, provide strong evidence that cognition cannot be analyzed and understood by looking at computational processes alone, but that physical system-environment interaction needs to be taken into account. In this opinion article, we review recent progress in cognitive developmental science and robotics, and expand the notion of embodiment to include soft materials and body morphology in the big picture. We argue that we need to build our understanding of cognition from the bottom up; that is, all the way from how our body is physically constructed.

The detection of 'soft' materials by selective energy xray transmission imaging and computer tomography

R. Zwiggelaar, C.R. Bull, M.J. Mooney and S. Czarnes, 'The detection of 'soft' materials by selective energy xray transmission imaging and computer tomography', Journal of Agricultural Engineering Research 66 (3), 203-212 (1997)