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Molecules and assemblies of molecules with well-defined secondary structures have been designed and characterized by controllingnoncovalent interactions. By specifying intermolecular interactions, a class of information-storing molecular duplexes have been successfully developed. These H-bonded molecular duplexes demonstrate programmable, sequence-specificity and predictable, tunable stabilities. Based on these highly specific molecular zippers (or glues), a systematic approach todesigning self-assembled structures is now feasible. . | Eur. J. Biochem. 271 1416-1425 2004 FEBS 2004 doi 10.1111 j.1432-1033.2004.04062.x REVIEW ARTICLE Well-defined secondary structures Information-storing molecular duplexes and helical foldamers based on unnatural peptide backbones Adam R. Sanford Kazuhiro Yamato Xiaowu Yang Lihua Yuan Yaohua Han and Bing Gong Department of Chemistry University at Buffalo State University of New York Buffalo NY USA Molecules and assemblies of molecules with well-defined secondary structures have been designed and characterized by controlling noncovalent ieleraclioi . By i j iecifnigg intermolecular interactions a class of information-storing molecular duplexes have been successfully developed. These H-bonded molecular duplexes demonstrate programmable sequence-specificity and predictable tunable stabilities. Based on these highly specific molecular zippers or glues a systematic approach to designing self-assembled structures is now feasible. Duplex-directed formation of b-sheets block copolymers and templated organic reactions have been realized. By specifyingintramolecular noncovalent interactions a backbone-rigidification strategy has been established leadingto unnatural molecular strands that adopt well-defined crescent or helical conformations. The generality of this backbone-rigidification strategy has been demonstrated in three different classes of unnatural oligomers oligoaramides oligoureas and oligo phenylene ethynylenes . Large nanosized cavities have been created based on the foldingof these helical foldamers. Tuningthe size of the nanocavities has been achieved without changing the underlyinghelical topology. These helical foldamers can serve as novel platforms for the systematic design of nanostructures. Keywords backbone rigidification duplex foldamer folding helix hydrogen bond nanocavity noncovalent self-assembly template. Introduction The assembly and foldingof biomolecules are arguably two of the most important features in nature. There is no doubt that without the
