The ring-opening metathesis polymerization (ROMP) was used to develop a new class of block copolymers toward biological detection with signal amplification. For this, three classes of ROMP monomers were synthesized: (i) luminescent and electrochemiluminescent transition-metal-containing monomers, with ruthenium, osmium, and iridium bipyridine units, (ii) biologically compatible monomers and macromonomers containing oligothylene glycol units, and (iii) bioconjugatable monomers as well as monomers containing the biorecognition unit biotin. ROMP was used to efficiently combine these monomers into amphiphilic di-and triblock copolymers. Self-assembly of these block copolymers in aqueous media generates micellar spherical assemblies, which contain a large number of luminescent transition-metal centers in their core, a biocompatible and biologically inert protecting shell, and biological recognition units or bioconjugatable groups on their periphery. These micelles can act as luminescent markers for biological molecules with potential for signal amplification. In addition, the monomers and polymers reported here can serve as useful biologically enabled building blocks for a number of applications, including drug delivery and tissue engineering.

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Six cyclometalated iridium(III) phenanthroimidazole complexes with different modifications to the imidazole phenanthroline ligand exhibit enhanced luminescence when bound to guanine (G-) quadruplex DNA sequences. The complexes bind with low micromolar affinity to human telomeric and c-myc sequences in a 1:1 complex:quadruplex stoichiometry. Due to the luminescence enhancement upon binding to G-quadruplex DNA, the complexes can be used as selective quadruplex indicators. In addition, the electrogenerated chemiluminescence of all complexes increases in the presence of specific G-quadruplex sequences, demonstrating potential for the development of an ECL-based G-quadruplex assay.

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Supporting information Contents 1. Experimental section: Reagents, methods and equipment 2. Synthesis of PEG-Biotin ROMP monomer 5 3. General procedure for polymerisation 4. Synthesis and characterization of Polymer 6 : (PEG) 3 -(Ir) 10 -(nBu) 10 5. Synthesis and characterization of Polymer 7 : (Bio) 1 -(PEG) 3 -(Ir) 10 -(nBu) 10 6. Synthesis and characterization of Polymer 8 : (BioPEG) 3 -(Ir) 10 -(nBu) 10 7. TEM images of micelles from polymers 6, 7 and 8 8. AFM images of micelles from polymers 6 9. Quantitation of amount of polymer bound to Streptavidin-coated magnetic beads 10. Scheme for microcontact printing of Streptavidin onto glass surfaces 1. Experimental section: Reagents, methods and equipment Reagents and supplies.