Dual-cavity basket promotes encapsulation in water in an allosteric fashion

Journal of the American Chemical Society
Shigui ChenJovica D Badjić

Abstract

We prepared dual-cavity basket 1 to carry six (S)-alanine residues at the entrance of its two juxtaposed cavities (289 Å(3)). With the assistance of (1)H NMR spectroscopy and calorimetry, we found that 1 could trap a single molecule of 4 (K1 = 1.45 ± 0.40 × 10(4) M(-1), ITC), akin in size (241 Å(3)) and polar characteristics to nerve agent VX (289 Å(3)). The results of density functional theory calculations (DFT, M06-2X/6-31G*) and experiments ((1)H NMR spectroscopy) suggest that the negative homotropic allosterism arises from the guest forming C-H···π contacts with all three of the aromatic walls of the occupied basket's cavity. In response, the other cavity increases its size and turns rigid to prevent the formation of the ternary complex. A smaller guest 6 (180 Å(3)), akin in size and polar characteristics to soman (186 Å(3)), was also found to bind to dual-cavity 1, although giving both binary [1⊂6] and ternary [1⊂62] complexes (K1 = 7910 M(-1) and K2 = 2374 M(-1), (1)H NMR spectroscopy). In this case, the computational and experimental ((1)H NMR spectroscopy) results suggest that only two aromatic walls of the occupied basket's cavity form C-H···π contacts with the guest to render the singly occupied host flexible enough t...Continue Reading

References

Jan 30, 2003·Journal of the American Chemical Society·Pall ThordarsonAlan E Rowan
Aug 28, 2003·Journal of the American Chemical Society·Nathan C GianneschiArnold L Rheingold
Dec 18, 2003·Journal of the American Chemical Society·Gianfranco Ercolani
Apr 14, 2004·Chemistry : a European Journal·Jovica D BadjićJ Fraser Stoddart
Sep 15, 2004·Angewandte Chemie·Pall ThordarsonRoeland J M Nolte
Jun 23, 2005·Journal of the American Chemical Society·Peter T CorbettSijbren Otto
Sep 21, 2005·Accounts of Chemical Research·Jovica D BadjićJ Fraser Stoddart
Jan 25, 2006·Angewandte Chemie·Lei Zhu, Eric V Anslyn
Mar 28, 2008·The Analyst·Justin A RiddleDongwhan Lee
Sep 12, 2009·Angewandte Chemie·Christopher A Hunter, Harry L Anderson
May 19, 2010·Nucleic Acids Research·Neil R Voss, Mark Gerstein
Dec 17, 2010·Nature Chemistry·Bruce C Gibb
Jan 21, 2011·Nature·Frank M Raushel
Mar 8, 2011·Organic Letters·Min-Tzu KaoYi-Hung Liu
Jun 15, 2011·Chemical Reviews·Kibong KimDavid G Churchill
Feb 22, 2012·Science·T AidaS I Stupp
Sep 8, 2012·Chemical Communications : Chem Comm·Katherine ChulviJosé-L Vivancos
Mar 1, 2013·The Journal of Organic Chemistry·Keith HermannJovica D Badjić
Apr 23, 2013·Organic & Biomolecular Chemistry·Dariush Ajami, Julius Rebek
Oct 5, 2013·Chemical Society Reviews·Jon R AskimKenneth S Suslick
Mar 13, 2014·Chemistry : a European Journal·Yian RuanJovica D Badjić
Apr 24, 2014·Journal of the American Chemical Society·William J Ramsay, Jonathan R Nitschke
May 20, 2014·Physical Chemistry Chemical Physics : PCCP·Motohiro NishioPinak Chakrabarti
Feb 27, 2015·Chemical Reviews·Guocan YuFeihe Huang
Mar 17, 2015·Nature Materials·Joseph E MondlochOmar K Farha

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Citations

Aug 12, 2016·Organic Letters·Yaowalak PratumyotJovica D Badjić
Aug 12, 2016·Journal of the American Chemical Society·Shigui ChenJovica D Badjić
Apr 21, 2017·Journal of the American Chemical Society·Carlo BravinCristiano Zonta
Jun 14, 2017·Chemistry : a European Journal·Lu WangJovica D Badjić
Jul 20, 2016·Organic & Biomolecular Chemistry·Hans-Jörg Schneider
Jan 7, 2020·Chemical Communications : Chem Comm·Weikun WangJovica D Badjić
Jul 12, 2019·Chemical Science·Weikun WangJovica D Badjić
Apr 22, 2021·ChemPlusChem·Ester ButeraGiuseppe Trusso Sfrazzetto
Oct 9, 2019·Journal of the American Chemical Society·Radoslav Z PavlovićJovica D Badjić
Nov 27, 2018·Journal of the American Chemical Society·Huang WuJ Fraser Stoddart
Aug 14, 2018·Journal of the American Chemical Society·Lei ZhiquanJovica D Badjić
Nov 12, 2021·Journal of the American Chemical Society·Ji-Min YangJulius Rebek

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