Enthalpy−Entropy Compensation Reveals Solvent Reorganization as a Driving Force for Supramolecular Encapsulation in Water

Leung, Dennis; Bergman, Robert G.; Raymond, Kenneth N.

doi:10.1021/ja075975z

Cited by 148 publications

(132 citation statements)

References 61 publications

(120 reference statements)

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“…Similar to the literature 5,13,53,54 , the host-guest system under discussion showed a good linear correlation (correlation coefficient: r ¼ 0.98) between DH°and TDS° (Supplementary Fig. S4).…”

Section: Discussionsupporting

confidence: 85%

Macromolecular semi-rigid nanocavities for cooperative recognition of specific large molecular shapes

et al. 2013

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Molecular shape recognition for larger guest molecules (typically over 1 nm) is a difficult task because it requires cooperativity within a wide three-dimensional nanospace coincidentally probing every molecular aspect (size, outline shape, flexibility and specific groups). Although the intelligent functions of proteins have fascinated many researchers, the reproduction by artificial molecules remains a significant challenge. Here we report the construction of large, well-defined cavities in macromolecular hosts. Through the use of semi-rigid dendritic phenylazomethine backbones, even subtle differences in the shapes of large guest molecules (up to B2 nm) may be discriminated by the cooperative mechanism. A conformationally fixed complex with the best-fitting guest is supported by a three-dimensional model based on a molecular simulation. Interestingly, the simulated cavity structure also predicts catalytic selectivity by a ruthenium porphyrin centre, demonstrating the high shape persistence and wide applicability of the cavity.

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Section: Discussionsupporting

confidence: 85%

Macromolecular semi-rigid nanocavities for cooperative recognition of specific large molecular shapes

et al. 2013

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“…For example, hydrogen bonds or metal coordination is frequently used to give a molecule, or a supramolecule, a well-defined structure. This is particularly true in regard to self-assembly, where groups capable of hydrogen bonding [26][27][28][29][30][31][32] or metal coordination [33][34][35][36][37][38][39][40][41][42][43][44][45] are powerful supramolecular motifs. But some translation-from the organic phase to the aqueous phase-is required here.…”

Section: High-definition Molecular and Supramolecular Structurementioning

confidence: 99%

Van Der Waals Interactions and the Hydrophobic Effect

Gibb

2011

Chemosensors

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“…Whereas guest encapsulation has been reported in a variety of media, association processes of organic guests are generally more thermodynamically favorable in water (22,23). Central to these studies is the notion that the displacement of a high-energy water cluster from a receptor drives guest association, and in some cases, subsequent catalysis.…”

mentioning

confidence: 99%

Protein-like proton exchange in a synthetic host cavity

Hart‐Cooper

Sgarlata

Perrin

et al. 2015

Proc. Natl. Acad. Sci. U.S.A.

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The mechanism of proton exchange in a metal-ligand enzyme active site mimic (compound 1) is described through amide hydrogendeuterium exchange kinetics. The type and ratio of cationic guest to host in solution affect the rate of isotope exchange, suggesting that the rate of exchange is driven by a host whose cavity is occupied by water. Rate constants for acid-, base-, and watermediated proton exchange vary by orders of magnitude depending on the guest, and differ by up to 200 million-fold relative to an alanine polypeptide. These results suggest that the unusual microenvironment of the cavity of 1 can dramatically alter the reactivity of associated water by magnitudes comparable to that of enzymes.W ater-mediated proton transfer in molecular cavities plays an essential role in the function of nature's remarkable metabolic machinery (1, 2). Of the broad diversity of enzymecatalyzed reactions, those involving transfer of hydrogen are ubiquitous and of high fundamental importance (3). For instance, ATP synthase employs an internal chain of water molecules to mediate proton transfer across an electrochemical gradient (4, 5). This process drives ATP synthesis, which allows organisms to broadly meet their basic energy needs. Recent studies of tunneling in enzymatic hydron transfer reactions have other far-reaching and broad implications, namely the importance of the dynamic enzyme motions in driving catalysis (6, 7).Of the methods used to study hydron transfer, kinetic studies of the mechanisms of amide hydrogen-deuterium exchange (HDX) have helped to elucidate the dynamic interactions between water and protein surfaces that are central to the unique capabilities of enzymes (8-13). Noncovalent interactions, such as electrostatic effects and hydrogen bonding, have also been shown to exert a significant influence on amide HDX rates. These properties are manifest in amide HDX rate constants that can vary by a factor of a billion for residues on the same protein (8). How these variations arise, and how such a property could be harnessed to drive enzyme-like reactivity, remain challenging questions.In a growing effort to emulate the efficacy of biological receptors and enzymes, studies of the preparative, guest-binding, and catalytic properties of synthetic assemblies have been pursued (14-21). Whereas guest encapsulation has been reported in a variety of media, association processes of organic guests are generally more thermodynamically favorable in water (22, 23). Central to these studies is the notion that the displacement of a high-energy water cluster from a receptor drives guest association, and in some cases, subsequent catalysis. However, despite the abundance of structural data documenting diverse water clusters encapsulated in various host cavities, mechanistic descriptions of the dynamic processes between water and host are rare (24-32).As part of the broader field of synthetic hosts previously mentioned, our group has developed a class of biologically inspired, anionic K 12 Ga 4 L 6 assemblies that exhibit cat...

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Enthalpy−Entropy Compensation Reveals Solvent Reorganization as a Driving Force for Supramolecular Encapsulation in Water

Cited by 148 publications

References 61 publications

Macromolecular semi-rigid nanocavities for cooperative recognition of specific large molecular shapes

Macromolecular semi-rigid nanocavities for cooperative recognition of specific large molecular shapes

Van Der Waals Interactions and the Hydrophobic Effect

Protein-like proton exchange in a synthetic host cavity

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