Homochiral oligomers with highly flexible backbones form stable H-bonded duplexes

Núñez‐Villanueva, Diego; Hunter, Christopher A.

doi:10.1039/c6sc02995g

Cited by 35 publications

(31 citation statements)

References 85 publications

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“…The association constants in Table 1 were used to calculate EM i for this system as 19 ± 3 mM, which is consistent with values of supramolecular effective molarities we have measured for other hydrogen bonded duplexes 31,34–36,38,39. The equilibrium constant for closing the duplex is given by and is 40 for this system, which implies that the duplex is fully closed and only 2% of the species populate the partially-bound open state o -AD·AD .…”

Section: Resultssupporting

confidence: 80%

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Building blocks for recognition-encoded oligoesters that form H-bonded duplexes

Szczypiński

Hunter

2019

Chem. Sci.

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Section: Resultssupporting

confidence: 80%

“…For the very flexible backbone shown in Fig. 2(a), the values of EM i and EM p are 10 mM to 30 mM, and the duplex channel dominates for length complementary homo-oligomers 34. For the very rigid backbone shown in Fig.…”

Section: Introductionmentioning

confidence: 94%

Building blocks for recognition-encoded oligoesters that form H-bonded duplexes

Szczypiński

Hunter

2019

Chem. Sci.

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“…1). [13][14][15][16][17][18][19][20][21] Hydrogen bonding interactions between sequence-complementary oligomers leads to formation of stable duplexes in organic solvents for a wide range of molecular designs based on different synthesis, backbone and recognition modules.…”

Section: Introductionmentioning

confidence: 99%

Emergent supramolecular assembly properties of a recognition-encoded oligoester

2019

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The sequences of oligomeric molecules equipped with interacting side-chains encode the threedimensional structure, the supramolecular assembly properties, and ultimately function. In an attempt to replicate the duplex forming properties of nucleic acids, an oligoester containing an alternating sequence of hydrogen bonding donor (D) and acceptor (A) residues was synthesised. Characterisation of assembly properties of the ADAD oligomer revealed a supramolecular architecture that resembles the kissing stem-loops motif found in folded RNA. NMR dilution and melting experiments in chloroform and 1,1,2,2-tetrachloroethane show that intramolecular hydrogen bonding interactions between the terminal phenol and phosphine oxide recognition sites in the ADAD 4-mer lead to 1,4-folding. This folded stemloop structure can be denatured to give the single strand by heating. At higher concentrations or lower temperatures, the stem-loop dimerises via intermolecular hydrogen bonding interactions between the two inner recognition sites, leading to a kissing stem-loops structure. The results suggest a rich supramolecular chemistry for these recognition-encoded oligoesters and lay strong foundations for the future development of new functional materials based on synthetic information molecules.

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“…11 Figure 1 shows the systems reported to date. Four different backbones have been prepared using either reductive amination or photochemical thiol–ene coupling.…”

Section: Introductionmentioning

confidence: 99%

H-Bond Self-Assembly: Folding versus Duplex Formation

et al. 2017

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Linear oligomers equipped with complementary H-bond donor (D) and acceptor (A) sites can interact via intermolecular H-bonds to form duplexes or fold via intramolecular H-bonds. These competing equilibria have been quantified using NMR titration and dilution experiments for seven systems featuring different recognition sites and backbones. For all seven architectures, duplex formation is observed for homo-sequence 2-mers (AA·DD) where there are no competing folding equilibria. The corresponding hetero-sequence AD 2-mers also form duplexes, but the observed self-association constants are strongly affected by folding equilibria in the monomeric states. When the backbone is flexible (five or more rotatable bonds separating the recognition sites), intramolecular H-bonding is favored, and the folded state is highly populated. For these systems, the stability of the AD·AD duplex is 1–2 orders of magnitude lower than that of the corresponding AA·DD duplex. However, for three architectures which have more rigid backbones (fewer than five rotatable bonds), intramolecular interactions are not observed, and folding does not compete with duplex formation. These systems are promising candidates for the development of longer, mixed-sequence synthetic information molecules that show sequence-selective duplex formation.

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Homochiral oligomers with highly flexible backbones form stable H-bonded duplexes

Abstract: Highly flexible oligomers make stable duplexes, when conformational mobility is not significantly restricted in the bound state.

Cited by 35 publications

References 85 publications

Building blocks for recognition-encoded oligoesters that form H-bonded duplexes

Building blocks for recognition-encoded oligoesters that form H-bonded duplexes

Emergent supramolecular assembly properties of a recognition-encoded oligoester

H-Bond Self-Assembly: Folding versus Duplex Formation

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