Synthesis of weakly-chelating monomers and copolymerization with N-isopropylacrylamide to provide ratiometric metal ion sensing polymers

ANYL 438

Roy P. Planalp, roy.planalp@unh.edu1, Daniel P. Kennedy, dpk2@unh.edu1, John O. Osambo, josambo@cisunix.unh.edu1, W. Rudolf Seitz1, Aaron Atkinson2, and Shawn C. Burdette, shawn.burdette@uconn.edu2. (1) Department of Chemistry, University of New Hampshire, Durham, NH 03824, (2) Department of Chemistry, University of Connecticut, 55 North Eagleville Road, Storrs, CT 06269
A variety of novel aminopyridyl, bipyridyl and iminodiacetate monomers with vinyl or acroyl groups have been prepared.  These are designed to weakly complex di- and trivalent 3d-transition-metal ions.  These monomers are selected to bind Cu(II) and Zn(II) with formation constants of 106 to 1010, while the double-bond functionalities are chosen to allow their incorporation into a swellable, lightly-crosslinked poly(N-isopropylacrylamide) [poly(NIPA)] which also contains fluorescence energy transfer (FRET) donor-acceptor pairs.  Metal detection ensues by a monitoring the swelling state of the polymer with FRET turn-on/off, and provide a ratiometric indication of metal-binding.  The synthesis and purification of these monomers in moderate to high yields will be described.  The apparent affinities of STYRYLIDA and MABIPY for Cu(II) and Zn(II) using napthalene-anthracene based FRET pair in poly(NIPA) will be presented.