Bottom-Up Characterization and Self-Assembly of Electrogenerated Chemiluminescence Active Ruthenium Nanospheres

An approach to electrogenerated chemiluminescence (ECL) signal enhancement, utilizing the highly tailorable ring-opening metathesis polymerization (ROMP) to generate novel ECL active nanoscale structures is explored. The strategy involves integrating into a single polymer multiple copies of an analogue of the established ECL luminophore, tris(2,2'-bipyridine)ruthenium(II) (Ru(bpy)(3)(2+)). Through the addition of hydrophobic and hydrophilic functional groups to the polymer architecture, these ECL active block copolymers are engineered to self-assemble when exposed to aqueous environments. Self-assembled ruthenium nanospheres generated through this methodology were found to demonstrate drastic signal amplification properties compared to their non-assembled polymer counterparts. Characterization methodologies conducted throughout the bottom-up synthesis of the nanospheres, utilizing the ECL reference of Ru(bpy)(3)(2+), facilitated investigating the origins of the nanosphere's signal enhancement.