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Science 7 July 2006:
Vol. 313. no. 5783, pp. 80 - 83
DOI: 10.1126/science.1127884

Reports

Probing the Solvent-Assisted Nucleation Pathway in Chemical Self-Assembly

Pascal Jonkheijm,1* Paul van der Schoot,2 Albertus P. H. J. Schenning,1{dagger} E. W. Meijer1{dagger}

Hierarchical self-assembly offers a powerful strategy for producing molecular nanostructures. Although widely used, the mechanistic details of self-assembly processes are poorly understood. We spectroscopically monitored a nucleation process in the self-assembly of p-conjugated molecules into helical supramolecular fibrillar structures. The data support a nucleation-growth pathway that gives rise to a remarkably high degree of cooperativity. Furthermore, we characterize a helical transition in the nucleating species before growth. The self-assembly process depends strongly on solvent structure, suggesting that an organized shell of solvent molecules plays an explicit role in rigidifying the aggregates and guiding them toward further assembly into bundles and/or gels.

1 Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of Technology, Post Office Box 513, 5600 MB Eindhoven, Netherlands.
2 Polymer Physics Group, Eindhoven University of Technology, Post Office Box 513, 5600 MB Eindhoven, Netherlands.

* Present address: Chemical Biology, Max Planck Institute for Molecular Physiology, Otto Hahnstrasse 11, 44227 Dortmund, Germany.

{dagger} To whom correspondence should be addressed. E-mail: e.w.meijer{at}tue.nl (E.W.M.); a.p.h.j.schenning{at}tue.nl (A.P.H.J.S.)

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