Effects of turn-structure on folding and entanglement in artificial molecular overhand knots
| Autor: | Iñigo J. Vitorica-Yrezabal, David A. Leigh, Lucian Pirvu, Fredrik Schaufelberger, Yiwei Song, Zoe Ashbridge |
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| Jazyk: | angličtina |
| Rok vydání: | 2020 |
| Předmět: |
Circular dichroism
Quantitative Biology::Biomolecules Materials science 010405 organic chemistry Stacking General Chemistry Nuclear magnetic resonance spectroscopy 010402 general chemistry 01 natural sciences Mathematics::Geometric Topology Protein tertiary structure 0104 chemical sciences 3. Good health Turn (biochemistry) Folding (chemistry) Crystallography Chemistry Knot (unit) Molecular knot |
| Zdroj: | Song, Y, Schaufelberger, F, Ashbridge, Z, Pirvu, L, Vitorica-yrezabal, I J & Leigh, D A 2020, ' Effects of turn-structure on folding and entanglement in artificial molecular overhand knots ', Chemical Science, vol. 12, no. 5, pp. 1826-1833 . https://doi.org/10.1039/D0SC05897A Chemical Science |
| Popis: | The length and constitution of spacers linking three 2,6-pyridinedicarboxamide units in a molecular strand influence the tightness of the resulting overhand (open-trefoil) knot that the strand folds into in the presence of lanthanide(iii) ions. The use of β-hairpin forming motifs as linkers enables a metal-coordinated pseudopeptide with a knotted tertiary structure to be generated. The resulting pseudopeptide knot has one of the highest backbone-to-crossing ratios (BCR)—a measure of knot tightness (a high value corresponding to looseness)—for a synthetic molecular knot to date. Preorganization in the crossing-free turn section of the knot affects aromatic stacking interactions close to the crossing region. The metal-coordinated pseudopeptide knot is compared to overhand knots with other linkers of varying tightness and turn preorganization, and the entangled architectures characterized by NMR spectroscopy, ESI-MS, CD spectroscopy and, in one case, X-ray crystallography. The results show how it is possible to program specific conformational properties into different key regions of synthetic molecular knots, opening the way to systems where knotting can be systematically incorporated into peptide-like chains through design. Spacers linking 2,6-pyridinedicarboxamide units influence the tightness of the corresponding lanthanide-coordinated overhand knot. β-Hairpin forming motifs generate a metal-coordinated pseudopeptide with a knotted tertiary structure. |
| Databáze: | OpenAIRE |
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