Multivalent display on linear platforms
is used by many biomolecular
systems to effectively interact with their corresponding binding partners
in a dose-responsive and ultrasensitive manner appropriate to the
biological system at hand. Synthetic supramolecular multivalent displays
offer a matching approach for the modular and bottom-up construction
and systematic study of dynamic 1D materials. Fundamental studies
into multivalent interactions between such linear, 1D materials have
been lacking because of the absence of appropriate modular nanoplatforms.
In this work we interfaced two synthetic multivalent linear nanoplatforms
based on a dynamic supramolecular polymer, formed by hybrid discotic-oligonucleotide
monomers, and a series of complementary DNA-duplex-based multivalent
ligands, also with appended short oligonucleotides. The combination
of these two multivalent nanoplatforms provides for the first time
entry to study multivalent effects in dynamic 1D systems, of relevance
for the conceptual understanding of multivalency in biology and for
the generation of novel multivalent biomaterials. Together the two
nanoscaffolds provide easy access to libraries of multivalent ligands
with tunable affinities. The DNA scaffold allows for exact control
over valency and spatial ligand distribution, and the discotic supramolecular
polymer allows for dynamic adaptation and control over receptor density.
The interaction between the two nanoplatforms was studied as a function
of ligand interaction strength, valency, and density. Usage of the
enhancement parameter β allowed quantification of the effects
of ligand valency and affinity. The results reveal a generalized principle
of additive binding increments. Receptor density is shown to be crucially
and nonlinearly correlated to complex formation, leading to ultrasensitive
responses. The results reveal that, not unlike biomolecular signaling,
high density multivalent display of receptors is crucial for functionally
increased affinities.