Registro de acceso restringido Este recurso no está disponible en acceso abierto por política de la editorial. No obstante, se puede acceder al texto completo desde la Universitat Jaume I o si el usuario cuenta con suscripción. Registre d'accés restringit Aquest recurs no està disponible en accés obert per política de l'editorial. No obstant això, es pot accedir al text complet des de la Universitat Jaume I o si l'usuari compta amb subscripció. Restricted access item This item isn't open access because of publisher's policy. The full--text version is only available from Jaume I University or if the user has a running suscription to the publisher's contents.

This paper reports the use of a range of amino acids to construct diverse gelators, employing structures in which Boc-protected amino acids are attached to either end of an aliphatic diamine spacer chain. The choice of amino acid determines whether nanoscale self-assembly takes place and controls the properties of the resultant material, while the function of the amino acid (e.g., the optical properties of tryptophan) is translated into the self-assembled nanostructured gel.

This article reports the covalent capture of self-assembled gel-phase materials using alkene metathesis. Gels assembled from a gelator functionalized with peripheral alkene groups were reacted with Grubbs' second generation catalyst, added as a solution to the top of the gel and allowed to diffuse into the material for 24 h. Using this approach, the fibrillar self-assembled network was covalently captured, yielding a large amount of insoluble material that was robust, thermally stable, and highly swellable in solvents compatible with the gelator. Scanning electron microscopy demonstrated that the insoluble metathesized material contained nanoscale fibers, which were aligned into rigid fiber bundles on drying. When the gelator was assembled in the presence of a second non-cross-linkable gelator, self-sorting took place, giving rise to two independent gelator networks. Metathesis then generated an insoluble material in which the individual gel fibers of the cross-linkable gelator were captured, whereas the nonreactive gelator could be washed away. Intriguingly, using this approach appeared to hinder the alignment of gel fibers into rigid fiber bundles. Instead, individual, well-defined, robust gelator nanofibers were visualized in the dried materials. In addition, the material synthesized this way appeared to be even more highly porous and swellable on the addition of solvent. In summary, this article demonstrates that metathesis is an effective way to capture nanostructured gel-phase materials covalently, with the judicious choice of additives helping to control the morphology and behavior of the materials generated. This approach to nanofabrication could ultimately give rise to nanostructured polymeric materials with a wide range of applications.