Different and Often Opposing Forces Drive the Encapsulation and Multiple Exterior Binding of Charged Guests to a M 4 L 6 Supramolecular Vessel in Water

Sgarlata, Carmelo; Mugridge, Jeffrey S.; Pluth, Michael D.; Zito, Valeria; Arena, Giuseppe; Raymond, Kenneth N.

doi:10.1002/chem.201703202

Different and Often Opposing Forces Drive the Encapsulation and Multiple Exterior Binding of Charged Guests to a M ₄ L ₆ Supramolecular Vessel in Water

Journal Article · Tue Nov 07 23:00:00 EST 2017 · Chemistry - A European Journal

DOI:https://doi.org/10.1002/chem.201703202· OSTI ID:1408154

Sgarlata, Carmelo ^[1]; Mugridge, Jeffrey S. ^[1]; Pluth, Michael D. ^[1]; Zito, Valeria ^[2]; Arena, Giuseppe ^[3]; ^[1]

Department of Chemistry University of California, Berkeley and Chemical Science Division, Lawrence Berkeley National Laboratory Berkeley California 94720-1460 USA
Istituto di Biostrutture e Bioimmagini CNR, UOS Catania Via P. Gaifami 18 95125 Catania Italy
Dipartimento di Scienze Chimiche Università degli Studi di Catania Viale A. Doria 6 95125 Catania Italy

Abstract

The supramolecular assembly [Ga ₄ L ₆ ] ¹²⁻ acts as a nanoscale flask to mediate the reactivity of encapsulated reactive guests and also functions as a catalyst to carry out enzyme‐like chemical transformations. The guest binding to the interior cavity and exterior of this host is difficult to untangle because multiple equilibria occur in solution, and only when refining simultaneously data obtained from different techniques, such as NMR, UV/Vis, and calorimetry, can the accurate solution thermodynamics of these host–guest systems be determined. This study reports the driving forces for the inclusion and stepwise exterior guest binding of different aliphatic quaternary ammonium guests to the [Ga ₄ L ₆ ] ¹²⁻ assembly. Encapsulation into the host cavity was found to be an entropy‐driven process, whereas exterior ion association is driven either by enthalpically favorable attractive forces or by the entropy gain due to desolvation, depending on guest size and character. The analysis of the energetics of reaction may help predicting and understanding the intimate role and contribution of the transition state in those rate‐accelerated reactions involving this supramolecular assembly as an enzyme‐like molecular flask.

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1408154

Journal Information:: Chemistry - A European Journal, Journal Name: Chemistry - A European Journal Journal Issue: 66 Vol. 23; ISSN 0947-6539

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

References (56)

Selbstorganisation eines supramolekularen tetraedrischen M4L6-Clusters Caulder, Dana L.; Powers, Ryan E.; Parac, Tatjana N. Angewandte Chemie, Vol. 110, Issue 13-14 https://doi.org/10.1002/(SICI)1521-3757(19980703)110:13/14<1940::AID-ANGE1940>3.0.CO;2-J	journal	July 1998
The Self-Assembly of a Predesigned Tetrahedral M₄L₆ Supramolecular Cluster Caulder, Dana L.; Powers, Ryan E.; Parac, Tatjana N. Angewandte Chemie International Edition, Vol. 37, Issue 13-14, p. 1840-1843 https://doi.org/10.1002/(SICI)1521-3773(19980803)37:13/14<1840::AID-ANIE1840>3.0.CO;2-D	journal	August 1998
Wechselwirkungen mit aromatischen Ringen in chemischen und biologischen Erkennungsprozessen Meyer, Emmanuel A.; Castellano, Ronald K.; Diederich, François Angewandte Chemie, Vol. 115, Issue 11 https://doi.org/10.1002/ange.200390290	journal	March 2003
Funktionale molekulare Reaktionskolben: neuartige Eigenschaften und Reaktionen in diskreten, selbstorganisierten Wirtmolekülen Yoshizawa, Michito; Klosterman, Jeremy K.; Fujita, Makoto Angewandte Chemie, Vol. 121, Issue 19 https://doi.org/10.1002/ange.200805340	journal	April 2009
Enzymnachbildungen auf der Basis supramolekularer Koordinationschemie Wiester, Michael J.; Ulmann, Pirmin A.; Mirkin, Chad A. Angewandte Chemie, Vol. 123, Issue 1 https://doi.org/10.1002/ange.201000380	journal	October 2010
Selektive Wirt-Gast-Bindung von Anionen ohne Hilfe von Wasserstoffbrücken: die Entropie als Designwerkzeug Ursu, Andrei; Schmidtchen, Franz P. Angewandte Chemie, Vol. 124, Issue 1 https://doi.org/10.1002/ange.201106018	journal	November 2011
Neues zum hydrophoben Effekt - Studien mit supramolekularen Komplexen zeigen hochenergetisches Wasser als nichtkovalente Bindungstriebkraft Biedermann, Frank; Nau, Werner M.; Schneider, Hans-Jörg Angewandte Chemie, Vol. 126, Issue 42 https://doi.org/10.1002/ange.201310958	journal	July 2014
Interactions with Aromatic Rings in Chemical and Biological Recognition Meyer, Emmanuel A.; Castellano, Ronald K.; Diederich, François Angewandte Chemie International Edition, Vol. 42, Issue 11 https://doi.org/10.1002/anie.200390319	journal	March 2003
Functional Molecular Flasks: New Properties and Reactions within Discrete, Self-Assembled Hosts Yoshizawa, Michito; Klosterman, Jeremy K.; Fujita, Makoto Angewandte Chemie International Edition, Vol. 48, Issue 19, p. 3418-3438 https://doi.org/10.1002/anie.200805340	journal	April 2009
Enzyme Mimics Based Upon Supramolecular Coordination Chemistry Wiester, Michael J.; Ulmann, Pirmin A.; Mirkin, Chad A. Angewandte Chemie International Edition, Vol. 50, Issue 1 https://doi.org/10.1002/anie.201000380	journal	October 2010
Selective Host-Guest Binding of Anions without Auxiliary Hydrogen Bonds: Entropy as an Aid to Design Ursu, Andrei; Schmidtchen, Franz P. Angewandte Chemie International Edition, Vol. 51, Issue 1 https://doi.org/10.1002/anie.201106018	journal	November 2011
The Hydrophobic Effect Revisited-Studies with Supramolecular Complexes Imply High-Energy Water as a Noncovalent Driving Force Biedermann, Frank; Nau, Werner M.; Schneider, Hans-Jörg Angewandte Chemie International Edition, Vol. 53, Issue 42 https://doi.org/10.1002/anie.201310958	journal	July 2014
Origins of Large Rate Enhancements in the Nazarov Cyclization Catalyzed by Supramolecular Encapsulation Hastings, Courtney J.; Bergman, Robert G.; Raymond, Kenneth N. Chemistry - A European Journal, Vol. 20, Issue 14 https://doi.org/10.1002/chem.201303885	journal	February 2014
Complexation of biologically active amines by a water-soluble calix[5]arene: A nanocalorimetric investigation Arena, Giuseppe; Pappalardo, Andrea; Pappalardo, Sebastiano Journal of Thermal Analysis and Calorimetry, Vol. 121, Issue 3 https://doi.org/10.1007/s10973-015-4522-3	journal	March 2015
Molecular recognition of organic anions by a water-soluble calix[4]arene: Evidence for enthalpy–entropy compensation Bonaccorso, Carmela; Ciadamidaro, Antonio; Zito, Valeria Thermochimica Acta, Vol. 530 https://doi.org/10.1016/j.tca.2011.12.014	journal	February 2012
Global Multi-Method Analysis of Affinities and Cooperativity in Complex Systems of Macromolecular Interactions Zhao, Huaying; Schuck, Peter Analytical Chemistry, Vol. 84, Issue 21 https://doi.org/10.1021/ac302357w	journal	September 2012
Quantifying High-Affinity Binding of Hydrophobic Ligands by Isothermal Titration Calorimetry Krainer, Georg; Broecker, Jana; Vargas, Carolyn Analytical Chemistry, Vol. 84, Issue 24 https://doi.org/10.1021/ac3025575	journal	November 2012
Untangling the Diverse Interior and Multiple Exterior Guest Interactions of a Supramolecular Host by the Simultaneous Analysis of Complementary Observables Sgarlata, Carmelo; Raymond, Kenneth N. Analytical Chemistry, Vol. 88, Issue 13 https://doi.org/10.1021/acs.analchem.6b01684	journal	June 2016
Experimental Binding Energies in Supramolecular Complexes Biedermann, Frank; Schneider, Hans-Jörg Chemical Reviews, Vol. 116, Issue 9 https://doi.org/10.1021/acs.chemrev.5b00583	journal	May 2016
Cationic Noncovalent Interactions: Energetics and Periodic Trends Rodgers, M. T.; Armentrout, P. B. Chemical Reviews, Vol. 116, Issue 9 https://doi.org/10.1021/acs.chemrev.5b00688	journal	March 2016
More Chemistry in Small Spaces Ajami, Dariush; Rebek, Julius Accounts of Chemical Research, Vol. 46, Issue 4 https://doi.org/10.1021/ar300038r	journal	May 2012
Stereochemistry in Subcomponent Self-Assembly Castilla, Ana M.; Ramsay, William J.; Nitschke, Jonathan R. Accounts of Chemical Research, Vol. 47, Issue 7 https://doi.org/10.1021/ar5000924	journal	April 2014
Proton-Mediated Chemistry and Catalysis in a Self-Assembled Supramolecular Host Pluth, Michael D.; Bergman, Robert G.; Raymond, Kenneth N. Accounts of Chemical Research, Vol. 42, Issue 10 https://doi.org/10.1021/ar900118t	journal	October 2009
Supramolecular Catalysis in Metal–Ligand Cluster Hosts Brown, Casey J.; Toste, F. Dean; Bergman, Robert G. Chemical Reviews, Vol. 115, Issue 9 https://doi.org/10.1021/cr4001226	journal	April 2015
Complexation Thermodynamics of Cyclodextrins Rekharsky, Mikhail V.; Inoue, Yoshihisa Chemical Reviews, Vol. 98, Issue 5 https://doi.org/10.1021/cr970015o	journal	July 1998
Diffusion of a Highly Charged Supramolecular Assembly: Direct Observation of Ion Association in Water ¹ Pluth, Michael D.; Tiedemann, Bryan E. F.; van Halbeek, Herman Inorganic Chemistry, Vol. 47, Issue 5 https://doi.org/10.1021/ic7020885	journal	March 2008
Structural Consequences of Anionic Host−Cationic Guest Interactions in a Supramolecular Assembly Pluth, Michael D.; Johnson, Darren W.; Szigethy, Géza Inorganic Chemistry, Vol. 48, Issue 1 https://doi.org/10.1021/ic8012848	journal	January 2009
Enthalpically driven cyclophane-arene inclusion complexation: solvent-dependent calorimetric studies Smithrud, David B.; Wyman, Tara B.; Diederich, Francois Journal of the American Chemical Society, Vol. 113, Issue 14 https://doi.org/10.1021/ja00014a038	journal	July 1991
Molecular Recognition and Stabilization of Iminium Ions in Water Dong, Vy M.; Fiedler, Dorothea; Carl, Barbara Journal of the American Chemical Society, Vol. 128, Issue 45 https://doi.org/10.1021/ja0657915	journal	November 2006
Making Amines Strong Bases: Thermodynamic Stabilization of Protonated Guests in a Highly-Charged Supramolecular Host ¹ Pluth, Michael D.; Bergman, Robert G.; Raymond, Kenneth N. Journal of the American Chemical Society, Vol. 129, Issue 37 https://doi.org/10.1021/ja072654e	journal	September 2007
Extraction of Hydrophobic Species into a Water-Soluble Synthetic Receptor Hooley, Richard J.; Van Anda, Hillary J.; Rebek, Julius Journal of the American Chemical Society, Vol. 129, Issue 44 https://doi.org/10.1021/ja0727058	journal	November 2007
The Hydrophobic Effect Drives the Recognition of Hydrocarbons by an Anionic Metal−Ligand Cluster ¹ Biros, Shannon M.; Bergman, Robert G.; Raymond, Kenneth N. Journal of the American Chemical Society, Vol. 129, Issue 40 https://doi.org/10.1021/ja075236i	journal	October 2007
Enthalpy−Entropy Compensation Reveals Solvent Reorganization as a Driving Force for Supramolecular Encapsulation in Water Leung, Dennis H.; Bergman, Robert G.; Raymond, Kenneth N. Journal of the American Chemical Society, Vol. 130, Issue 9 https://doi.org/10.1021/ja075975z	journal	March 2008
Enzymelike Catalysis of the Nazarov Cyclization by Supramolecular Encapsulation Hastings, Courtney J.; Pluth, Michael D.; Bergman, Robert G. Journal of the American Chemical Society, Vol. 132, Issue 20 https://doi.org/10.1021/ja102633e	journal	May 2010
Alkane Lengths Determine Encapsulation Rates and Equilibria Jiang, Wei; Ajami, Dariush; Rebek, Julius Journal of the American Chemical Society, Vol. 134, Issue 19 https://doi.org/10.1021/ja302669y	journal	April 2012
Release of High-Energy Water as an Essential Driving Force for the High-Affinity Binding of Cucurbit[ n ]urils Biedermann, Frank; Uzunova, Vanya D.; Scherman, Oren A. Journal of the American Chemical Society, Vol. 134, Issue 37 https://doi.org/10.1021/ja303309e	journal	September 2012
Temporary and Permanent Trapping of the Metastable Twisted Conformer of an Overcrowded Chromic Alkene via Encapsulation Takezawa, Hiroki; Murase, Takashi; Fujita, Makoto Journal of the American Chemical Society, Vol. 134, Issue 42 https://doi.org/10.1021/ja308101a	journal	October 2012
Selective Monoterpene-like Cyclization Reactions Achieved by Water Exclusion from Reactive Intermediates in a Supramolecular Catalyst Hart-Cooper, William M.; Clary, Kristen N.; Toste, F. Dean Journal of the American Chemical Society, Vol. 134, Issue 43 https://doi.org/10.1021/ja308254k	journal	October 2012
Solvent and Pressure Effects on the Motions of Encapsulated Guests: Tuning the Flexibility of a Supramolecular Host Mugridge, Jeffrey S.; Zahl, Achim; van Eldik, Rudi Journal of the American Chemical Society, Vol. 135, Issue 11 https://doi.org/10.1021/ja309949q	journal	March 2013
Cucurbit[8]uril and Blue-Box: High-Energy Water Release Overwhelms Electrostatic Interactions Biedermann, Frank; Vendruscolo, Michele; Scherman, Oren A. Journal of the American Chemical Society, Vol. 135, Issue 39 https://doi.org/10.1021/ja407951x	journal	September 2013
Rationally Designed Cooperatively Enhanced Receptors To Magnify Host–Guest Binding in Water Gunasekara, Roshan W.; Zhao, Yan Journal of the American Chemical Society, Vol. 137, Issue 2 https://doi.org/10.1021/ja510823h	journal	January 2015
Aza Cope Rearrangement of Propargyl Enammonium Cations Catalyzed By a Self-Assembled “Nanozyme” Hastings, Courtney J.; Fiedler, Dorothea; Bergman, Robert G. Journal of the American Chemical Society, Vol. 130, Issue 33 https://doi.org/10.1021/ja8013055	journal	August 2008
External and Internal Guest Binding of a Highly Charged Supramolecular Host in Water: Deconvoluting the Very Different Thermodynamics Sgarlata, Carmelo; Mugridge, Jeffrey S.; Pluth, Michael D. Journal of the American Chemical Society, Vol. 132, Issue 3 https://doi.org/10.1021/ja9056739	journal	January 2010
Selective Encapsulation of Aqueous Cationic Guests into a Supramolecular Tetrahedral [M ₄ L ₆ ] ¹² ^- Anionic Host ¹ Parac, Tatjana N.; Caulder, Dana L.; Raymond, Kenneth N. Journal of the American Chemical Society, Vol. 120, Issue 31 https://doi.org/10.1021/ja981690y	journal	August 1998
Concerning the thermodynamics of molecular recognition in aqueous and organic media. Evidence for significant heat capacity effects Stauffer, David A.; Barrans, Richard E.; Dougherty, Dennis A. The Journal of Organic Chemistry, Vol. 55, Issue 9 https://doi.org/10.1021/jo00296a038	journal	April 1990
A supramolecular approach to combining enzymatic and transition metal catalysis Wang, Z. Jane; Clary, Kristen N.; Bergman, Robert G. Nature Chemistry, Vol. 5, Issue 2 https://doi.org/10.1038/nchem.1531	journal	January 2013
Integration and global analysis of isothermal titration calorimetry data for studying macromolecular interactions Brautigam, Chad A.; Zhao, Huaying; Vargas, Carolyn Nature Protocols, Vol. 11, Issue 5 https://doi.org/10.1038/nprot.2016.044	journal	April 2016
Water-soluble, self-assembling container molecules: an update Laughrey, Zachary; Gibb, Bruce C. Chem. Soc. Rev., Vol. 40, Issue 1 https://doi.org/10.1039/C0CS00030B	journal	January 2011
Molecular containers assembled through the hydrophobic effect Jordan, Jacobs H.; Gibb, Bruce C. Chemical Society Reviews, Vol. 44, Issue 2 https://doi.org/10.1039/C4CS00191E	journal	January 2015
Factors driving the self-assembly of water-soluble calix[4]arene and gemini guests: a combined solution, computational and solid-state study Bonaccorso, Carmela; Brancatelli, Giovanna; Forte, Giuseppe RSC Adv., Vol. 4, Issue 96 https://doi.org/10.1039/C4RA09353D	journal	January 2014
Stereochemistry and thermodynamics of the inclusion of aliphatic and aromatic anionic guests in a tetracationic calix[4]arene in acidic and neutral aqueous solutions Sgarlata, Carmelo; Bonaccorso, Carmela; Gulino, Fabio Giuseppe New Journal of Chemistry, Vol. 33, Issue 5 https://doi.org/10.1039/b901164c	journal	January 2009
Protein-like proton exchange in a synthetic host cavity Hart-Cooper, William M.; Sgarlata, Carmelo; Perrin, Charles L. Proceedings of the National Academy of Sciences, Vol. 112, Issue 50 https://doi.org/10.1073/pnas.1515639112	journal	November 2015
Acid Catalysis in Basic Solution: A Supramolecular Host Promotes Orthoformate Hydrolysis Pluth, M. D.; Bergman, R. G.; Raymond, K. N. Science, Vol. 316, Issue 5821 https://doi.org/10.1126/science.1138748	journal	April 2007
Allosteric Supramolecular Triple-Layer Catalysts Yoon, H. J.; Kuwabara, J.; Kim, J. -H. Science, Vol. 330, Issue 6000 https://doi.org/10.1126/science.1193928	journal	September 2010
A supramolecular microenvironment strategy for transition metal catalysis Kaphan, D. M.; Levin, M. D.; Bergman, R. G. Science, Vol. 350, Issue 6265 https://doi.org/10.1126/science.aad3087	journal	December 2015
A synthetic and NMR conformational study of spiro cyclic quaternary ammonium salts Aitken, R. Alan; Philp, Eilidh F.; Riddell, Frank G. Arkivoc, Vol. 2002, Issue 3 https://doi.org/10.3998/ark.5550190.0003.306	journal	January 2002

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Different and Often Opposing Forces Drive the Encapsulation and Multiple Exterior Binding of Charged Guests to a M ₄ L ₆ Supramolecular Vessel in Water