Heparin,
an anionic biomacromolecule, is routinely used as an anticoagulant
during medical surgery to prevent blood clot formation and in the
treatment of several heart, lung, and circulatory disorders having
a higher risk of blood clotting. We herein report supramolecular polymeric
nanoassemblies of cationic pyrene-tagged bis-imidazolium amphiphiles
for heparin detection with high sensitivity and selectivity in aqueous
buffer, plasma, and serum media. The nano-assemblies exhibited cyan-green
excimeric emission in aqueous media, and their multivalent array of
positive surface charges allowed them to form co-assemblies with heparin,
resulting in significantly enhanced emission. This provided a convenient
method for heparin detection in buffer at nanomolar concentrations,
and most notably, a ratiometric fluorescence response was obtained
even in highly competitive 100% human serum and 100% human plasma
in a clinically relevant concentration range. Moreover, using the
heparin-based luminescent co-assemblies, protamine sulfate, a clinically
administered antidote to heparin, was also detected in 100% human
serum and 100% human plasma at sub-micromolar concentrations.