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Synthesis of crystals with a programmable kinetic barrier to nucleation

Schulman, Rebecca and Winfree, Erik (2007) Synthesis of crystals with a programmable kinetic barrier to nucleation. Proceedings of the National Academy of Sciences of the United States of America, 104 (39). pp. 15236-15241. ISSN 0027-8424. PMCID PMC1986573. doi:10.1073/pnas.0701467104.

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A central goal of chemistry is to fabricate supramolecular structures of defined function and composition. In biology, control of supramolecular synthesis is often achieved through precise control over nucleation and growth processes: A seed molecule initiates growth of a structure, but this growth is kinetically inhibited in the seed's absence. Here we show how such control can be systematically designed into self-assembling structures made of DNA tiles. These structures, "zig-zag ribbons," are designed to have a fixed width but can grow arbitrarily long. Under slightly supersaturated conditions, theory predicts that elongation is always favorable but that nucleation rates decrease exponentially with increasing width. We confirm experimentally that although ribbons of different widths have similar thermodynamics, nucleation rates decrease for wider ribbons. It is therefore possible to program the nucleation rate by choosing a ribbon width. The presence of a seed molecule, a stabilized version of the presumed critical nucleus, removes the kinetic barrier to nucleation of a ribbon. Thus, we demonstrate the ability to grow supramolecular structures from rationally designed seeds, while suppressing spurious nucleation. Control over DNA tile nucleation allows for proper initiation of algorithmic crystal growth, which could lead to the high-yield synthesis of micrometer-scale structures with complex programmed features. More generally, this work shows how a self-assembly subroutine can be initiated.

Item Type:Article
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URLURL TypeDescription CentralArticle Information
Schulman, Rebecca0000-0003-4555-3162
Winfree, Erik0000-0002-5899-7523
Additional Information:© 2007 by the National Academy of Sciences. Edited by Alan R. Fersht, University of Cambridge, Cambridge, United Kingdom, and approved July 19, 2007 (received for review February 16, 2007). Published online before print September 19, 2007. We thank Paul Rothemund, Bernie Yurke, Peng Yin, Ho-Lin Chen, Rizal Hariadi, Rick Flagan, and Rob Barish for insightful discussions and encouragement. This work was supported by National Aeronautics and Space Administration Astrobiology Grant NNG06GA50G and National Science Foundation Grant NANO/CCF-0432193. Author contributions: R.S. and E.W. designed research; R.S. performed research; R.S. and E.W. analyzed data; and R.S. and E.W. wrote the paper. The authors declare no conflict of interest. Freely available online through the PNAS open access option. This article contains supporting information online at
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Subject Keywords:algorithmic self-assembly, DNA nanotechnology, self-assembly, supramolecular chemistry
Issue or Number:39
PubMed Central ID:PMC1986573
Record Number:CaltechAUTHORS:SCHUpnas07
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:8837
Deposited By: Archive Administrator
Deposited On:20 Sep 2007
Last Modified:08 Nov 2021 20:53

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