Engineering hydrogen‐bonded duplexes

Abstract

Based on several simple, readily available building blocks, oligoamide strands carrying various arrays of hydrogen-bond donors and acceptors, i.e. hydrogen-bonding sequences, have been designed and synthesized. Detailed characterization indicates that these oligoamide strands associate via their hydrogen-bonding edges into doubled stranded pairs (duplexes), which are characterized by programmable sequence specificity and adjustable stability. Using these hydrogen-bonded duplexes as association units, supramolecular structures, such as β-sheets and non-covalent block copolymers, are obtained by simply mixing the corresponding components. Recently, by incorporating reversible covalent interactions into these hydrogen-bonded duplexes, sequence-specific formation of covalently linked structures has been realized under thermodynamic conditions, which has opened an entirely new avenue to the development of previously unknown dynamic covalent structures such as various block copolymers.

Binding Mechanisms in Supramolecular Complexes

“…[345] quantities DG AA or DG DD on the one hand and the repulsive quantities DG AD or DG AD on the other is consistent with Coulomb forces being the source of the secondary interactions, which should be numerically equal in the two cases by virtue of identical partial charges and geometric positioning. [357] Nucleic acids themselves represent building blocks for the construction of higher molecular weight associates through numerous D-A combinations, [358] as well as for the development of new materials through selfassociation. This was observed, for example, with various DDA-D·AADA heterodimers.…”

“…These can be realized synthetically (examples: 25-28), [356] and used to develop new types of polymers. [357] Nucleic acids themselves represent building blocks for the construction of higher molecular weight associates through numerous D-A combinations, [358] as well as for the development of new materials through selfassociation. [359] The production of nanoscale materials from DNA double strands and the corresponding quadruplexes also rests on such complementary hydrogen bonds.…”

Bindungsmechanismen in supramolekularen Komplexen

“…Diese lassen sich auch synthetisch realisieren (Beispiele 25-28), [356] auch zur Gewinnung von neuartigen Polymeren. [357] Nucleinsäuren selber dienen als Bausteine für die Konstruktion höhermolekularer Assoziate über zahlreiche D-A-Kombinationen, [358] auch für die Ent-wicklung neuer Materialien durch Selbstassoziation. [359] Auch die Herstellung nanoskaliger Materialien aus DNA-Doppelsträngen und entsprechenden Quadruplexen beruht auf solchen komplementären Wasserstoffbrücken.…”

Surprising impact of remote groups on the folding–unfolding and dimer-chain equilibria of bifunctional H-bonding unimers

“…10 Compound 1 , consisting of two unsymmetrical 4-H-bonded units 11,12 covalently linked in a head-to-head fashion, represents one such design of this series. If adopting an extended conformation, a molecule of 1 could only partially overlap with another one via four intermolecular H-bonds, and would thus lead to linear H-bonded polymers.…”