This proposal will elaborate strategies for the synthesis of programmed synthetic macromolecules that are instructed to self-assemble and self-organize into complex functional nanoarchitectures with chemical organization on all levels. This concept is currently available only in biological systems. A programmed synthetic macromolecule is a macromolecule with precise primary structure, that includes monodisperse molecular weight distribution, composition, sequence distribution and stereochemistry, that is instructed to self-assemble into the 3-dimensional (3-D) nanoarchitecture required to provide a specific function. This architecture must be controlled at its seconday, tertiary and quaternary levels and is called complex functional architecture. Currently available polymerization methods cannot be used to design programmed macromolecules. Therefore, an accelerated design strategy via retrostructural analysis will be used to develop libraries of programmed macromolecules via combinations of divergent and convergent iterative synthetic methods. Simultaneously, a self-interrupted polymerization method will be elaborated. This method is expected to apply to all chain and step polymerizations known and generate the first polymerization method that will produce monodisperse synthetic macromolecules. Libraries of programmed macromolecules that self-assemble into various biological mimics such us porous proteins, hollow globular protein, supramolecular capsules, chiral supramolecular nanostructures from achiral building blocks, and supramolecular nanospheres that exhibit intramolecular chirality will be developed. These nanoarchitectures will facilitate access to extremely efficient biological functions such as transmembrane channels, antimicrobials, reversible encapsulation and delivery, enzymatic-like catalysis, electronic materials, stochastic sensing, new sources of energy, separation processes, memory effects and also amplify already known material properties. NON-TECHNICAL SUMMARY: Current approaches to materials with specific properties are cost and time inefficient and generate only minimal improvements. This proposal intends to apply biological nanostructural principles to the design of synthetic nanomaterials with specific functions. An accelerated design strategy that involves expertise from chemistry, physics and biology with collaboration between universities in US and abroad, governmental laboratories and industry will develop the principles required to amplify materials properties by up to several orders of magnitude. Extremely efficient separation processes, enzymatic-like catalysis, sensing, new sources of energy and new approaches to medicine are expected to emerge from this research. This research will change our way to design materials properties at the most fundamental level and affect accordingly the education of a new generation of graduate, undergraduate and high school students.
