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Beyond the Molecular Frontier: Challenges for Chemistry and Chemical Engineering (2003)
Board on Chemical Sciences and Technology (BCST)

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Beyond the Molecular Frontier: Challenges for Chemistry and Chemical Engineering

tures create new possibilities for applications, a direction that will continue to drive materials chemistry.

High-molecular-weight polymers can be useful as solid materials and in solution, and lower molecular weight polymers can make liquids that are unusual in character. Synthetic adhesives illustrate liquid-phase materials that cross-link or polymerize when they set. Water-based paints are another example, liquids with suspended solid polymer particles that form uniform solid films during drying. So-called liquid crystals illustrate another exciting example of complex fluid materials; these are liquid-phase materials made up of anisotropic, usually fairly rigid, molecules of high aspect ratio that have strong electric dipole moments. Such molecules are prone to adopt preferred orientations, especially under the influence of surfaces, electric fields, and flow processes. Control over preferred orientations gives high anisotropic strength of materials and switchable optical properties, making them useful in displays such as those on digital watches and laptop computers.

Multicomponent systems having molecules of macromolecular size and heterogeneous composition can be exquisitely sensitive to the delicate balance of intermolecular forces. The fine interplay among a suite of noncovalent interactions (e.g., steric, electrostatic, electrodynamic, and solvation forces) dictates microstructure and dynamics. Molecular organization and interaction cause collective and cooperative behavior to dictate macroscopic properties. Often the balance of forces is such that self-assembly occurs to generate aggregates, arrays, or other supramolecular structures. Large molecular size enables amplification of a small segmental effect into a large intermolecular effect. Self-assembly can amplify the small forces between small objects to produce large-scale structures useful for macroscopic creations for patterning, sieving, sorting, detecting, or growing materials, biological molecules, or chemicals. Learning to understand and harness intermolecular interactions in multicomponent polymer and composite systems offers huge challenges, as well as opportunities to mimic nature, which has learned to do this in many instances.

Self-assembled monolayers (SAMs) are ordered, two-dimensional crystals or quasi-crystals formed by adsorption and ordering of organic molecules or metal complexes on planar substrates. Development of these monolayers is based on early studies in which chemists learned to attach chemicals to surfaces—for purposes ranging from adhesion to chromatography to electrochemistry—but often without strong ordering in the monolayers. The ordered structures have made it possible to develop a rational surface science of organic materials. They provide the best current example of the power of self-assembly to make possible the design of the properties of materials. They have made routine the control of wetting, adhesion, and corrosion in certain systems, and—through soft lithography—they have provided a new approach to microfabrication that is uniquely chemical in its versatility. They have also greatly advanced the field of biomaterials by making it possible to control the interface between cells and synthetic materials at the molecular level.

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