Guest packing motifs within a supramolecular nanocapsule and a covalent analogue.

Two hosts that utilize the hydrophobic effect to assemble and/or encapsulate guest molecules were studied. The hosts, octa-acid (OA) and hexalene diamine-linked octa-acid (HOA), were shown to complex a broad range of n-alkanes up to n-hexacosane (C26H54). A combination of (1)H NMR, NMR diffusion, COSY, and NOESY experiments revealed four different guest packing motifs, depending on the size of the guest and the nature of the host. As a function of guest size, smooth transitions from one motif to the next were observed and allowed qualification of their relative stabilities. Furthermore, although the two hosts engender ostensibly identical encapsulation environments, their different assembly properties lead to quite distinct packing-motif profiles, i.e., how the motifs change as a function of guest size.

[1]  B. Gibb,et al.  Dynamics of a supramolecular capsule assembly with pyrene. , 2012, Journal of the American Chemical Society.

[2]  K. Raymond,et al.  High-turnover supramolecular catalysis by a protected ruthenium(II) complex in aqueous solution. , 2011, Journal of the American Chemical Society.

[3]  J. Rebek,et al.  Bent alkanes in a new thiourea-containing capsule. , 2011, Journal of the American Chemical Society.

[4]  Simin Liu,et al.  An improved synthesis of ‘octa-acid’ deep-cavity cavitand , 2011, Supramolecular chemistry.

[5]  Y. Ko,et al.  U-shaped conformation of alkyl chains bound to a synthetic receptor cucurbit[8]uril. , 2011, Chemistry, an Asian journal.

[6]  S. Rick,et al.  Kinetic resolution of constitutional isomers controlled by selective protection inside a supramolecular nanocapsule. , 2010, Nature chemistry.

[7]  Y. Ko,et al.  Unconventional U-shaped conformation of a bolaamphiphile embedded in a synthetic host. , 2010, Chemical communications.

[8]  M. Fujita,et al.  Naphthalene Diels-Alder in a self-assembled molecular flask. , 2010, Journal of the American Chemical Society.

[9]  J. Rebek,et al.  Recognition and organocatalysis with a synthetic cavitand receptor. , 2009, Journal of the American Chemical Society.

[10]  E. Yamashita,et al.  The Structure of Rat Liver Vault at 3.5 Angstrom Resolution , 2009, Science.

[11]  Michael D. Pluth,et al.  Supramolecular catalysis of orthoformate hydrolysis in basic solution: an enzyme-like mechanism. , 2008, Journal of the American Chemical Society.

[12]  Takumi Yamaguchi,et al.  Asymmetric [2 + 2] olefin cross photoaddition in a self-assembled host with remote chiral auxiliaries. , 2008, Journal of the American Chemical Society.

[13]  Y. Ko,et al.  U-shaped conformation of alkyl chains bound to a synthetic host. , 2008, Angewandte Chemie.

[14]  J. Rebek,et al.  Organocatalysis in a synthetic receptor with an inwardly directed carboxylic acid. , 2008, Journal of the American Chemical Society.

[15]  Takumi Yamaguchi,et al.  Highly selective photomediated 1,4-radical addition to o-quinones controlled by a self-assembled cage. , 2008, Angewandte Chemie.

[16]  Hao Sun,et al.  Calorimetric Analysis of the 1:1 Complexes Formed between a Water-soluble Deep-cavity Cavitand, and Cyclic and Acyclic Carboxylic Acids , 2008 .

[17]  Michael D. Pluth,et al.  Catalytic deprotection of acetals in basic solution with a self-assembled supramolecular "nanozyme". , 2007, Angewandte Chemie.

[18]  Y. Takashima,et al.  External stimulus-responsive supramolecular structures formed by a stilbene cyclodextrin dimer. , 2007, Journal of the American Chemical Society.

[19]  B. Clantin,et al.  Structure of the Membrane Protein FhaC: A Member of the Omp85-TpsB Transporter Superfamily , 2007, Science.

[20]  J. Rebek.  Contortions of encapsulated alkyl groups. , 2007, Chemical communications.

[21]  Takumi Yamaguchi,et al.  Unusual [2+4] and [2+2] cycloadditions of arenes in the confined cavity of self-assembled cages. , 2007, Journal of the American Chemical Society.

[22]  B. Gibb,et al.  Straight-chain alkanes template the assembly of water-soluble nano-capsules. , 2007, Chemical communications.

[23]  Michael D. Pluth,et al.  Acid Catalysis in Basic Solution: A Supramolecular Host Promotes Orthoformate Hydrolysis , 2007, Science.

[24]  B. Gibb,et al.  Templated assembly of water-soluble nano-capsules: inter-phase sequestration, storage, and separation of hydrocarbon gases. , 2006, Journal of the American Chemical Society.

[25]  J. Rebek,et al.  Coiled molecules in spring loaded devices. , 2006, Journal of the American Chemical Society.

[26]  D. Fiedler,et al.  Supramolecular catalysis of unimolecular rearrangements: substrate scope and mechanistic insights. , 2006, Journal of the American Chemical Society.

[27]  Yong Chen,et al.  Cooperative binding and multiple recognition by bridged bis(beta-cyclodextrin)s with functional linkers. , 2006, Accounts of chemical research.

[28]  J. Rebek,et al.  Experimental and computational probes of the space in a self-assembled capsule. , 2006, Proceedings of the National Academy of Sciences of the United States of America.

[29]  K. Wüthrich,et al.  GroEL‐GroES‐mediated protein folding , 2006, Chemical reviews.

[30]  M. Tamura,et al.  Diels-Alder in Aqueous Molecular Hosts: Unusual Regioselectivity and Efficient Catalysis , 2006, Science.

[31]  J. Rebek,et al.  Deep cavitands provide organized solvation of reactions. , 2005, Journal of the American Chemical Society.

[32]  Yoram Cohen,et al.  Diffusion NMR spectroscopy in supramolecular and combinatorial chemistry: an old parameter--new insights. , 2005, Angewandte Chemie.

[33]  J. Rebek,et al.  Helical folding of alkanes in a self-assembled, cylindrical capsule. , 2004, Journal of the American Chemical Society.

[34]  B. Gibb,et al.  Well-defined, organic nanoenvironments in water: the hydrophobic effect drives a capsular assembly. , 2004, Journal of the American Chemical Society.

[35]  J. Rebek,et al.  Encapsulation induces helical folding of alkanes. , 2003, Angewandte Chemie.

[36]  J. Rebek,et al.  Helical Conformation of Alkanes in a Hydrophobic Cavitand , 2003, Science.

[37]  Stuart J Rowan,et al.  Dynamic covalent chemistry. , 2002, Angewandte Chemie.

[38]  J. Rebek,et al.  Selectivity in an encapsulated cycloaddition reaction. , 2002, Organic letters.

[39]  J. Rebek,et al.  Self-Assembled Molecular Capsule Catalyzes a Diels−Alder Reaction , 1998 .

[40]  J. Rebek,et al.  Formation of Discrete, Functional Assemblies and Informational Polymers through the Hydrogen-Bonding Preferences of Calixarene Aryl and Sulfonyl Tetraureas , 1998 .

[41]  A. Horwich,et al.  The crystal structure of the asymmetric GroEL–GroES–(ADP)7 chaperonin complex , 1997, Nature.

[42]  J. Rebek,et al.  Acceleration of a Diels–Alder reaction by a self-assembled molecular capsule , 1997, Nature.

[43]  J C Sacchettini,et al.  Crystal structure of rat intestinal fatty-acid-binding protein. Refinement and analysis of the Escherichia coli-derived protein with bound palmitate. , 1989, Journal of molecular biology.