Protamine-Induced Supramolecular Self-Assembly of Red-Emissive Alkynylplatinum(II) 2,6-Bis(benzimidazol-2′-yl)pyridine Complex for Selective Label-Free Sensing of Heparin and Real-Time Monitoring of Trypsin Activity

A label-free detection assay is developed based on the design and synthesis of a new anionic alkynylplatinum(II) 2,6-bis(benzimidazol-2'-yl)pyridine complex with water-soluble pendants. With the aid of electrostatic interaction and noncovalent metal-metal and π-π stacking interactions, protamine is shown to induce supramolecular self-assembly of platinum(II) complexes with drastic UV-vis absorption and red emission changes. On the basis of the strong binding affinity of protamine and heparin, the ensemble has been further employed to probe heparin by monitoring the spectroscopic changes. Other than heparin, this ensemble can also detect the activity of trypsin, which can hydrolyze protamine into fragments, leading to the deaggregation of platinum(II) complexes. By modulation of the self-assembly properties of platinum(II) complexes via real-time UV-vis absorption and emission studies, the reported assay has been demonstrated to be a sensitive and selective detection method for trypsin, as well as trypsin inhibitor screening, which is essential for drug discovery.