Note to users. If you're seeing this message, it means that your browser cannot find this page's style/presentation instructions -- or possibly that you are using a browser that does not support current Web standards. Find out more about why this message is appearing, and what you can do to make your experience of our site the best it can be.

Science 6 April 2007:
Vol. 316. no. 5821, pp. 85 - 88
DOI: 10.1126/science.1138748
Prev | Table of Contents | Next

Reports

Acid Catalysis in Basic Solution: A Supramolecular Host Promotes Orthoformate Hydrolysis

Michael D. Pluth, Robert G. Bergman,* Kenneth N. Raymond*

Although many enzymes can promote chemical reactions by tuning substrate properties purely through the electrostatic environment of a docking cavity, this strategy has proven challenging to mimic in synthetic host-guest systems. Here, we report a highly charged, water-soluble, metal-ligand assembly with a hydrophobic interior cavity that thermodynamically stabilizes protonated substrates and consequently catalyzes the normally acidic hydrolysis of orthoformates in basic solution, with rate accelerations of up to 890-fold. The catalysis reaction obeys Michaelis-Menten kinetics and exhibits competitive inhibition, and the substrate scope displays size selectivity, consistent with the constrained binding environment of the molecular host.

Department of Chemistry, University of California, Berkeley, Berkeley, CA 94720, USA.

* To whom correspondence should be addressed. E-mail: rbergman{at}berkeley.edu (R.G.B.); raymond{at}socrates.berkeley.edu (K.N.R.)

Read the Full Text


THIS ARTICLE HAS BEEN CITED BY OTHER ARTICLES:
Molecular Recognition and Self-Assembly Special Feature: Self-assembled biomimetic [2Fe2S]-hydrogenase-based photocatalyst for molecular hydrogen evolution.
A. M. Kluwer, R. Kapre, F. Hartl, M. Lutz, A. L. Spek, A. M. Brouwer, P. W. N. M. van Leeuwen, and J. N. H. Reek (2009)
PNAS 106, 10460-10465
   Abstract »    Full Text »    PDF »
Molecular Recognition and Self-Assembly Special Feature: Encapsulation and characterization of proton-bound amine homodimers in a water-soluble, self-assembled supramolecular host.
M. D. Pluth, D. Fiedler, J. S. Mugridge, R. G. Bergman, and K. N. Raymond (2009)
PNAS 106, 10438-10443
   Abstract »    Full Text »    PDF »
White Phosphorus Is Air-Stable Within a Self-Assembled Tetrahedral Capsule.
P. Mal, B. Breiner, K. Rissanen, and J. R. Nitschke (2009)
Science 324, 1697-1699
   Abstract »    Full Text »    PDF »


To Advertise     Find Products

Science. ISSN 0036-8075 (print), 1095-9203 (online)