Well-defined secondary structures.

Molecules and assemblies of molecules with well-defined secondary structures have been designed and characterized by controlling noncovalent 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 to designing self-assembled structures is now feasible. Duplex-directed formation of beta-sheets, block copolymers and templated organic reactions have been realized. By specifying intramolecular noncovalent interactions, a backbone-rigidification strategy has been established, leading to 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 folding of these helical foldamers. Tuning the size of the nanocavities has been achieved without changing the underlying helical topology. These helical foldamers can serve as novel platforms for the systematic design of nanostructures.

[1]  Bing Gong,et al.  A new class of folding oligomers: Crescent oligoamides [4] , 2000 .

[2]  B. Gong,et al.  Evolution of Helical Foldamers , 2003 .

[3]  B. Jaun,et al.  γ2‐, γ3‐, and γ2,3,4‐Amino Acids, Coupling to γ‐Hexapeptides: CD Spectra, NMR Solution and X‐ray Crystal Structures of γ‐Peptides , 2002 .

[4]  E. W. Meijer,et al.  Quadruple hydrogen bonded systems. , 2003, Chemical communications.

[5]  E. W. Meijer,et al.  Self‐Complementarity Achieved through Quadruple Hydrogen Bonding , 1998 .

[6]  Annelise E Barron,et al.  Mimicry of bioactive peptides via non-natural, sequence-specific peptidomimetic oligomers. , 2002, Current opinion in chemical biology.

[7]  Richard D Smith,et al.  An extremely stable, self-complementary hydrogen-bonded duplex. , 2003, Chemical communications.

[8]  M. Krische,et al.  The covalent casting of one-dimensional hydrogen bonding motifs: toward oligomers and polymers of predefined topography. , 2001, Chemistry.

[9]  G. Whitesides,et al.  Noncovalent Synthesis: Using Physical-Organic Chemistry To Make Aggregates , 1995 .

[10]  S. Zimmerman,et al.  Heteroaromatic Modules for Self-Assembly Using Multiple Hydrogen Bonds , 2000 .

[11]  C. Hunter,et al.  Synthesis and recognition properties of aromatic amide oligomers: Molecular zippers , 2000 .

[12]  David N. Reinhoudt,et al.  Noncovalent Synthesis Using Hydrogen Bonding. , 2001, Angewandte Chemie.

[13]  J. Nowick,et al.  Designed molecules that fold to mimic protein secondary structures. , 1999, Current opinion in chemical biology.

[14]  Samuel H. Gellman,et al.  Foldamers: A Manifesto , 1998 .

[15]  Carsten Schmuck,et al.  Molecules with helical structure: how to build a molecular spiral staircase. , 2003, Angewandte Chemie.

[16]  Matthew J. Mio,et al.  A field guide to foldamers. , 2001, Chemical reviews.

[17]  B. Gong,et al.  A noncovalent approach to antiparallel β-sheet formation , 2002 .

[18]  S. Zimmerman,et al.  Self-Association without Regard to Prototropy. A Heterocycle That Forms Extremely Stable Quadruply Hydrogen-Bonded Dimers , 1998 .

[19]  B. Gong,et al.  Sequence specificity of hydrogen-bonded molecular duplexes. , 2001, The Journal of organic chemistry.

[20]  B Gong,et al.  Crescent oligoamides: from acyclic "macrocycles" to folding nanotubes. , 2001, Chemistry.

[21]  B. Gong,et al.  A Highly Stable, Six-Hydrogen-Bonded Molecular Duplex , 2000 .

[22]  Bing Gong,et al.  A new strategy for folding oligo(m-phenylene ethynylenes). , 2003, Chemical communications.

[23]  B Gong,et al.  Stable three-center hydrogen bonding in a partially rigidified structure. , 2001, Chemistry.

[24]  E. W. Meijer,et al.  STRONG DIMERIZATION OF UREIDOPYRIMIDONES VIA QUADRUPLE HYDROGEN BONDING , 1998 .

[25]  Douglas Philp,et al.  Self‐Assembly in Natural and Unnatural Systems , 1996 .

[26]  M. Ghadiri,et al.  Peptide Nanotubes and Beyond , 1998 .

[27]  M. Krische,et al.  Duplex oligomers defined via covalent casting of a one-dimensional hydrogen-bonding motif. , 2002, Journal of the American Chemical Society.

[28]  J. Rebek,et al.  Self-Assembling Capsules. , 1997, Chemical reviews.

[29]  B. Jaun,et al.  Probing the Helical Secondary Structure of Short‐Chain β‐Peptides , 1996 .

[30]  G. Whitesides,et al.  Molecular self-assembly and nanochemistry: a chemical strategy for the synthesis of nanostructures. , 1991, Science.

[31]  Kenji Kobayashi,et al.  The Structural and Thermodynamic Basis for the Formation of Self‐Assembled Peptide Nanotubes , 1995 .

[32]  H. Kagechika,et al.  Helical aromatic urea and guanidine , 1997 .

[33]  J S Moore,et al.  Solvophobically driven folding of nonbiological oligomers. , 1997, Science.

[34]  Yun-Dong Wu,et al.  Novel Turns and Helices in Peptides of Chiral α-Aminoxy Acids , 1999 .

[35]  T. J. Murray,et al.  New triply hydrogen bonded complexes with highly variable stabilities , 1992 .

[36]  S. Blechert,et al.  Recent developments in olefin cross-metathesis. , 2003, Angewandte Chemie.

[37]  S. Gellman,et al.  Intramolecular Hydrogen Bonding in Derivatives of .beta.-Alanine and .gamma.-Amino Butyric Acid; Model Studies for the Folding of Unnatural Polypeptide Backbones , 1994 .

[38]  R. Grubbs,et al.  The development of L2X2Ru=CHR olefin metathesis catalysts: an organometallic success story. , 2001, Accounts of chemical research.

[39]  J. Rebek,et al.  DYNAMICS OF ASSEMBLY AND GUEST EXCHANGE IN THE TENNIS BALL , 1998 .

[40]  Ulrich Hommel,et al.  β‐Peptides: Synthesis by Arndt‐Eistert homologation with concomitant peptide coupling. Structure determination by NMR and CD spectroscopy and by X‐ray crystallography. Helical secondary structure of a β‐hexapeptide in solution and its stability towards pepsin , 1996 .

[41]  E. W. Meijer,et al.  Cooperative Dynamics in Duplexes of Stacked Hydrogen-Bonded Moieties , 1999 .

[42]  T. J. Murray,et al.  Convenient Synthesis of 2-Amino-1,8-naphthyridines, Building Blocks for Host-Guest and Self-Assembling Systems , 1993 .

[43]  B. Iverson,et al.  Models of higher-order structure: foldamers and beyond. , 2001, Current opinion in chemical biology.

[44]  W. DeGrado,et al.  beta-Peptides: from structure to function. , 2001, Chemical reviews.

[45]  S. Michnick,et al.  Design of Secondary Structures in Unnatural Peptides: Stable Helical γ-Tetra-, Hexa-, and Octapeptides and Consequences of α-Substitution , 1998 .

[46]  David J. Hill,et al.  Helicogenicity of solvents in the conformational equilibrium of oligo(m-phenylene ethynylene)s: Implications for foldamer research , 2002, Proceedings of the National Academy of Sciences of the United States of America.

[47]  William L. Jorgensen,et al.  Importance of secondary interactions in triply hydrogen bonded complexes: guanine-cytosine vs uracil-2,6-diaminopyridine , 1990 .

[48]  A. Parrill,et al.  Solid Phase Synthesis and Secondary Structural Studies of (1→5) Amide-Linked Sialooligomers1 , 1998 .

[49]  Ivan Huc,et al.  Interconversion of single and double helices formed from synthetic molecular strands , 2000, Nature.

[50]  D. Seebach,et al.  β-Peptides: a surprise at every turn , 1997 .

[51]  E. W. Meijer,et al.  Facile synthesis of a chiral polymeric helix; folding by intramolecular hydrogen bonding. , 2004, Chemical communications.

[52]  Harold L. Ickes,et al.  A NEW APPROACH FOR THE DESIGN OF SUPRAMOLECULAR RECOGNITION UNITS : HYDROGEN-BONDED MOLECULAR DUPLEXES , 1999 .

[53]  Richard D. Smith,et al.  Duplex foldamers from assembly induced folding. , 2003, Journal of the American Chemical Society.

[54]  Thomas Szyperski,et al.  Creating nanocavities of tunable sizes: Hollow helices , 2002, Proceedings of the National Academy of Sciences of the United States of America.

[55]  Wolfram Saenger,et al.  Principles of Nucleic Acid Structure , 1983 .

[56]  J. Rebek Reversible Encapsulation and Its Consequences in Solution , 1999 .

[57]  G. Whitesides,et al.  Self-assembly based on the cyanuric acid-melamine lattice , 1990 .

[58]  William L. Jorgensen,et al.  OPLS potential functions for nucleotide bases. Relative association constants of hydrogen-bonded base pairs in chloroform , 1991 .