Naphthyridine-based helical foldamers and macrocycles: synthesis, cation binding, and supramolecular assemblies.
Unraveling the factors that control the conformation of molecular chains is of great interest both for understanding the shape of biological molecular strands and for designing artificial ones that adopt desired forms. Thus, a variety of artificial folding codons have been identified that enforce the formation, among others, of helices, strands, and loops, the major emphasis being on the shape of the foldamer. We report herein the synthesis and study of a family of foldamers and macrocycles based on the 1,8-naphthyridine and pyrimidine units, whose internal cavity is large enough to accommodate ionic substrates, and focus on the impact of guest binding within a cylindrical environment. Interestingly, the binding event within these large oligomers is translated to the outside of the receptors and affects the interaction of the overall complexes with the outside world. For instance, alkali cations bind to the one-turn helices and macrocycles to promote fibril formation and aggregation. Also, polyammonium substrates are able to tune the length of the overall helix assemblies and the rigidity of long oligomers. The reported data on one-turn, two-turn helices and macrocycles not only allows one to devise a model for the ion-controlled supramolecular assembly of such systems but also provides evidence that such controlled scaffolds bear promise in the design of complex systems.
Petitjean
Anne
A
Laboratoire de Chimie Supramoléculaire, Institut de Science et d'Ingénierie Supramoléculaires, Université Louis Pasteur, 8 Allée Gaspard Monge, BP 70028, 67083 Strasbourg Cedex, France.
Cuccia
Louis A
LA
Schmutz
Marc
M
Lehn
Jean-Marie
JM
D001665:Binding Sites; D002412:Cations / Q000737:chemistry; D002942:Circular Dichroism / Q000379:methods; D047028:Macrocyclic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D046911:Macromolecular Substances / Q000138:chemical synthesis / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy / Q000379:methods / Q000592:standards; D008958:Models, Molecular; D015394:Molecular Structure; D009287:Naphthyridines / Q000138:chemical synthesis* / Q000737:chemistry*; D010316:Particle Size; D033362:Powder Diffraction; D011743:Pyrimidines / Q000138:chemical synthesis* / Q000737:chemistry*; D012015:Reference Standards; D013237:Stereoisomerism
D002412:Cations; D047028:Macrocyclic Compounds; D046911:Macromolecular Substances; D009287:Naphthyridines; D011743:Pyrimidines