Chiral recognition at self-assembled multivalent (SAMul) nanoscale interfaces – enantioselectivity in polyanion binding

Chan, Ching Wan; Laurini, Eric; Posocco, Paola; Pricl, Sabrina; Smith, David K.

doi:10.1039/c6cc04470k

Cited by 17 publications

(24 citation statements)

References 37 publications

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“…We have reported that a chiral SAMul lysine ligand array can control polyanion binding . Interestingly, however, when using lysine ligands, chiral recognition of heparin does not always occur—Wang and Rabenstein reported that there was no impact of chirality in their peptide heparin binders, whilst we found that the precise structure of the self‐assembling system determined whether chiral recognition was achieved . In this new study, we wanted to gain a more detailed understanding of the chiral preferences of both heparin and DNA, and unambiguously understand, in thermodynamic terms, any inherent differences in the way these important polyanions interact with chiral nanoscale objects.…”

Section: Figuresupporting

confidence: 93%

“…The difference in binding free energy (Δ G bind ) between the best binder ( ld ) and the worst binder ( dl ) is large, at 5.7 kJ mol −1 . This is significantly larger than the 2.6 kJ mol −1 difference in Δ G bind that we observed previously for related systems with glycine instead of alanine units, suggesting that chiral alanine units help pre‐organise the lysine ligands for enantioselective recognition. More detailed thermodynamic analysis indicates that the difference between DNA binders is primarily a result of different enthalpies of binding (Δ H bind differs by up to 4.5 kJ mol −1 ).…”

Section: Figurementioning

confidence: 99%

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Enantiomeric and Diastereomeric Self‐Assembled Multivalent Nanostructures: Understanding the Effects of Chirality on Binding to Polyanionic Heparin and DNA

et al. 2018

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A family of four self-assembling lipopeptides containing Ala-Lys peptides attached to a C aliphatic chain were synthesised. These compounds form two enantiomeric pairs that bear a diastereomeric relationship to one another (C -l-Ala-l-Lys/C -d-Ala-d-Lys) and (C -d-Ala-l-Lys/C -l-Ala-d-Lys). These diastereomeric pairs have very different critical micelle concentrations (CMCs). The self-assembled multivalent (SAMul) systems bind biological polyanions as a result of the cationic lysine groups on their surfaces. For heparin binding, there was no significant enantioselectivity, but there was a binding preference for the diastereomeric assemblies with lower CMCs. Conversely, for DNA binding, there was significant enantioselectivity for systems displaying d-lysine ligands, with a further slight preference for attachment to l-alanine, with the CMC being irrelevant.

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Section: Figuresupporting

confidence: 93%

Section: Figurementioning

confidence: 99%

Enantiomeric and Diastereomeric Self‐Assembled Multivalent Nanostructures: Understanding the Effects of Chirality on Binding to Polyanionic Heparin and DNA

et al. 2018

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“…Communications 8532 www.angewandte.org binders (ll slightly better than dl). Thedifference in binding free energy (DG bind )b etween the best binder (ld)a nd the worst binder (dl)islarge,at5.7 kJ mol À1 .T his is significantly larger than the 2.6 kJ mol À1 difference in DG bind that we observed previously for related systems with glycine instead of alanine units, [19] suggesting that chiral alanine units help pre-organise the lysine ligands for enantioselective recognition. More detailed thermodynamic analysis indicates that the difference between DNAb inders is primarily ar esult of different enthalpies of binding (DH bind differs by up to 4.5 kJ mol À1 ).…”

Section: Angewandte Chemiementioning

confidence: 78%

Enantiomeric and Diastereomeric Self‐Assembled Multivalent Nanostructures: Understanding the Effects of Chirality on Binding to Polyanionic Heparin and DNA

et al. 2018

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Af amily of four self-assembling lipopeptides containing Ala-Lys peptides attached to aC 16 aliphatic chain were synthesised. These compounds form two enantiomeric pairs that bear ad iastereomeric relationship to one another (C 16 -l-Ala-l-Lys/C 16 -d-Ala-d-Lys) and (C 16 -d-Ala-l-Lys/C 16l-Ala-d-Lys). These diastereomeric pairs have very different critical micelle concentrations (CMCs). The self-assembled multivalent (SAMul) systems bind biological polyanions as ar esult of the cationic lysine groups on their surfaces.F or heparin binding,there was no significant enantioselectivity,but there was ab inding preference for the diastereomeric assemblies with lower CMCs.C onversely,f or DNAb inding,t here was significant enantioselectivity for systems displaying d-lysine ligands,with afurther slight preference for attachment to l-alanine,with the CMC being irrelevant.

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“…Extending this research further, chiral amino acid modifications were made to a very simple amphiphile (C 16 -Lys and C 16 -Gly-Lys). 68 The presence of a glycine spacer unit between Fig. 11 (top) TGD-G2 and (bottom) PAMAM-G2 dendrimers bound to heparin at a charge excess of 0.4 using MD modelling methods.…”

Section: Selectivity In Electrostatic Bindingtowards the Polyanion Worldmentioning

confidence: 99%

From fundamental supramolecular chemistry to self-assembled nanomaterials and medicines and back again – how Sam inspired SAMul

Smith

2018

Chem. Commun.

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This feature article provides a personal insight into the research from my group over the past 10 years. In particular, the article explains how, inspired in 2005 by meeting my now-husband, Sam, who had cystic fibrosis, and who in 2011 went on to have a double lung transplant, I took an active decision to follow a more applied approach to some of our research, attempting to use fundamental supramolecular chemistry to address problems of medical interest. In particular, our strategy uses self-assembly to fabricate biologically-active nanosystems from simple low-molecular-weight building blocks. These systems can bind biological polyanions in highly competitive conditions, allowing us to approach applications in gene delivery and coagulation control. In the process, however, we have also developed new fundamental principles such as self-assembled multivalency (SAMul), temporary 'on-off' multivalency, and adaptive/shape-persistent multivalent binding. By targeting materials with applications in drug formulation and tissue engineering, we have discovered novel self-assembling low-molecular-weight hydrogelators based on the industrially-relevant dibenzylidenesorbitol framework and developed innovative approaches to spatially-resolved gels and functional multicomponent hybrid hydrogels. In this way, taking an application-led approach to research has also delivered significant academic value and conceptual advances. Furthermore, beginning to translate fundamental supramolecular chemistry into real-world applications, starts to demonstrate the power of this approach, and its potential to transform the world around us for the better.

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Chiral recognition at self-assembled multivalent (SAMul) nanoscale interfaces – enantioselectivity in polyanion binding

Cited by 17 publications

References 37 publications

Enantiomeric and Diastereomeric Self‐Assembled Multivalent Nanostructures: Understanding the Effects of Chirality on Binding to Polyanionic Heparin and DNA

Enantiomeric and Diastereomeric Self‐Assembled Multivalent Nanostructures: Understanding the Effects of Chirality on Binding to Polyanionic Heparin and DNA

Enantiomeric and Diastereomeric Self‐Assembled Multivalent Nanostructures: Understanding the Effects of Chirality on Binding to Polyanionic Heparin and DNA

From fundamental supramolecular chemistry to self-assembled nanomaterials and medicines and back again – how Sam inspired SAMul

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