UV- and Thermally Triggered Ring-Opening Metathesis Polymerization for the Spatially Resolved Functionalization of Polymeric Monolithic Devices

Porous polymeric monolithic supports were prepared via electron beam-triggered free radical polymerization using a mixture of ethyl methacrylate and trimethylolpropane triacrylate in 2-propanol, 1-dodecanol and toluene. Bicyclo[2.2.1]hept-5-en-2-ylmethyl acrylate (1) was grafted onto these monolithic supports in a spatially resolved way with the aid of masks using both electron beam- (EB) and UV-triggered free radical polymerization. The thus immobilized norborn-2-ene-containing graft polymers were further treated with the 2(nd)-generation Grubbs initiator, i.e., RuCl(2)(PCy(3))(IMesH(2))(CHPh) (4) (IMesH(2) = 1,3-dimesitylimidazolin-2-ylidene), and then reacted with bicyclo[2.2.1] hept-5-en-2-ylmethyl pyrene-1-carboxylate (2). Alternatively, monoliths completely grafted with poly-1 were surface grafted with 2 in a spatially resolved way in the presence of a latent, UV-triggerable precatalyst, i.e., [Ru(IMesH(2))(CF(3)COO)(t-BuCN)(4)(+) CF(3)COO(-)] (5). Finally, to demonstrate the utility of this chemistry, a 2(nd)-generation Grubbs initiator-based approach was used to prepare a trypsin-functionalized monolith-containing chip device that allowed for the online digestion of N-alpha-benzoyl-L-argininethylester hydrochloride. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci 121: 2551-2558, 2011