Architecture of macromolecular network of soft functional materials: from structure to function.

An enhanced macromolecular nanofiber network and its implications have been developed by employing the understanding of its formation with an emphasis on its topological aspect. Using agarose aqueous solution as a typical example, the macromolecular nanofiber network of soft functional materials has been clearly visualized for the first time using the developed technique of field emission scanning electronic microscopy coupled with flash-freeze-drying. Both the systematic kinetic study and the image evidence indicates that the nanofiber network in soft functional materials such as agarose turns out to form through a self-expitaxial nucleation-controlled process. This new understanding enables us to engineer ultra functions of soft materials via nanofiber network architecture, which in turn opens up a new direction in nano fabrication.

Architecture of fiber network: from understanding to engineering of molecular gels.

A new approach of engineering of molecular gels was established on the basis of a nucleation-initiated network formation mechanism. A variety of gel network structures can be obtained by regulating the starting temperature of the sol-gel transition. This enables us to tune the network from the spherulitic domains pattern to the extensively interconnected fibrillar network. As the consequence of fibrous network structure turning, desirable rheological and other in-use properties of the materials can be obtained accordingly. This approach of micro-/nanostructural fabrication may open up a new route for micro-/nanofunctional materials engineering in general.

Architecture of a biocompatible supramolecular material by supersaturation-driven fabrication of its fiber network.

The architecture of a biocompatible organogel formed by gelation of a small molecule organic gelator, N-lauroyl-L-glutamic acid di-n-butylamide, in isostearyl alcohol was investigated based on a supersaturation-driven crystallographic mismatch branching mechanism. By controlling the supersaturation of the system, the correlation length that determines the mesh size of the fiber network was finely tuned and the rheological properties of the gel were engineered. This approach is of considerable significance for many gel-based applications, such as controlled release of drugs that requires precise control of the mesh size. A direct cryo-transmission electron microscopy (TEM) imaging technique capable of preserving the network structure was used to visualize its nanostructure.

Topology evolution and gelation mechanism of agarose gel.

Kinetics as well as the evolution of the agarose gel topology is discussed, and the agarose gelation mechanism is identified. Aqueous high melting (HM) agarose solution (0.5% w/v) is used as the model system. It is found that the gelation process can be clearly divided into three stages: induction stage, gelation stage, and pseudoequilibrium stage. The induction stage of the gelation mechanism is identified using an advanced rheological expansion system (ARES, Rheometric Scientific). When a quench rate as large as 30 deg C/min is applied, gelation seems to occur through a nucleation and growth mechanism with a well-defined induction time (time required for the formation of the critical nuclei which enable further growth). The relationship between the induction time and the driving force which is determined by the final setting temperature follows the 3D nucleation model. A schematic representation of the three stages of the gelation mechanism is given based on turbidity and rheological measurements. Aggregation of agarose chains is promoted in the polymer-rich phase and this effect is evident from the increasing mass/length ratio of the fiber bundles upon gelation. Continuously increasing pore size during gelation may be attributed to the coagulation of the local polymer-rich phase in order to achieve the global minimum of the free energy of the gelling system. The gel pore size determined using turbidity measurements has been verified by electrophoretic mobility measurements.

Preferential solvation stabilization for hydrophobic polymeric nanoparticle fabrication.

Preferential solvation of polymer molecules and strong EPD-EPA (EPD, electron pair donor; EPA, electron pair acceptor) interaction between solvent and nonsolvent molecules were found to be of great significance in the fabrication of two kinds of aromatic polyimide (AP) nanoparticles. Surfactant free yet stable AP nanoparticles were prepared using a liquid-liquid phase separation method. The stability of the AP nanoparticles can be achieved by the solvation multilayer resulting from a solvation stabilization chain in the form of nonsolvent --> solvent --> AP (a --> b denotes that component b is solvated by component a). The significance of this stabilization chain was identified by many comparative experiments using different types of molecular probes. On the other hand, the formation of AP nanoparticles was found to be governed by a nucleation process and therefore the particle size is controlled by the nucleation rate. A very high level of supersaturation can be attained under the intensive local motions induced by ultrasound, resulting in a very high nucleation rate. This effect was found to be extremely useful in the fabrication of sub-50 nm AP nanoparticles.