Cooperative phenomena, described by one-dimensional statistical physical methods, are observed between the enantiomeric characteristics of monomeric materials and the polymers they produce. The effect of minute energies associated with this amplified chirality, although currently not interpretable, can be easily measured. Nonlinear relationships between enantiomeric excess or enantiomeric content and polymer properties may offer the possibility of developing chiral catalysts and chiral chromatographic materials in which the burden of large enantiomeric excess or content may be considerably alleviated. New approaches to information and sensor technology may become possible.
An aqueous vesicular system that is switchable by electric potential without addition of any chemical redox agents into the solution is demonstrated using redox-responsive self-assembly of an amphiphilic rod-coil molecule consisting of a tetraaniline and a poly(ethylene glycol) block. The vesicle membrane is split by an oxidizing voltage into smaller pucklike micelles that can reassemble to form vesicles upon exposure to a reducing voltage. The switching mechanism is explained by the packing behavior of the tetraaniline units constituting the membrane core, which depends on their oxidation states.
This Account describes how stereochemical ideas focused on chirality have been directed widely across polymer science allowing experiments that could not be conducted on small molecules and leading to new insights and new kinds of materials. In one approach, a helical polymer was studied, and it was discovered how the chiral information necessary to choose helical sense is greatly amplified. In another approach, the racemization kinetics of atropisomers were used to characterize the restrictions to motion associated with a polyelectrolyte that forms clusters around hydrophobic groups in water and in an entirely different system, the glassy state formed by polymers.
A layer-by-layer deposition of two conducting polymers, each layer of which is a few tenths of nanometer thick, has been successfully performed to enhance the thermoelectric power factor of organic thin films.
A diblock copolymer consisting of poly(3-(triethoxysilyl)propylisocyanate) (PIC) and polystyrene(PS) was synthesized by anionic polymerization. A polymeric monolayer of the block copolymer was formed on silica substrates by various grafting techniques such as immersion, casting, or contact-printing. The PIC block adheres covalently to Si substrates in an in-plane fashion due to its extended rodlike conformation and reactivity to the silica. The polystyrene blocks aggregate to form mounds on the surface resulting in a new type of nanopatterned polymer brush. The self-limiting adsorption of the rod coils results in a thickness of about 5 nm regardless of the solution concentration and coating method. This particular property allowed microcontact printing directly onto silicon or glass substrates. The resulting surface morphology consisted of nanoscale domains given by the block copolymer and uniform thickness micropatterns transferred from the stamp within the printed area. This study offers a simple new method to prepare a covalent polymeric monolayer with nano- and micropatterns, which can be performed directly onto various silicon-based substrates.
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