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

Area of Science:

• Supramolecular chemistry
• Nanoscale science
• Biomaterials science

Background:

• Self-assembled multivalent (SAMul) ligands are crucial for molecular recognition.
• Functionalizing ligands with cationic amino acids like lysine is a common strategy for binding polyanions such as heparin and DNA.
• Controlling chiral recognition at the nanoscale is challenging but important for biological applications.

Purpose of the Study:

• To investigate the role of ligand structure in chiral discrimination.
• To explore the development of SAMul ligands with controlled chiral recognition capabilities.
• To understand the molecular mechanisms underlying chiral recognition at SAMul interfaces.

Main Methods:

• Synthesis of palmitic acid-based SAMul ligands functionalized with cationic l/d-lysine.
• Incorporation of a glycine spacer unit into the ligand structure.
• Binding studies with polyanionic heparin and DNA to assess affinity and specificity.
• Chiral discrimination assays to evaluate enantioselective binding.

Main Results:

• SAMul ligands with cationic lysine showed no chiral preference when binding heparin or DNA.
• The introduction of a glycine spacer unit into the SAMul ligand structure induced significant chiral discrimination.
• This represents a rare instance of controlled chiral recognition at a SAMul nanoscale interface.

Conclusions:

• Ligand design, specifically the inclusion of spacer units, is critical for achieving chiral recognition in SAMul systems.
• The developed SAMul ligands offer a new platform for enantioselective molecular recognition at the nanoscale.
• This work opens avenues for developing chiral-sensitive nanomaterials for various applications, including drug delivery and diagnostics.