title: Gel catalysts that switch on and off.
abstract: We report development of a polymer gel with a catalytic activity that can be switched on and off when the solvent composition is changed. The gel consists of two species of monomers. The major component, N-isopropylacrylamide, makes the gel swell and shrink in response to a change in composition of ethanol/water mixtures. The minor component, vinylimidazole, which is capable of catalysis, is copolymerized into the gel network. The reaction rate for catalytic hydrolysis of p-nitrophenyl caprylate was small when the gel was swollen. In contrast, when the gel was shrunken, the reaction rate increased 5 times. The activity changes discontinuously as a function of solvent composition, thus the catalysis can be switched on and off by an infinitesimal change in solvent composition. The kinetics of catalysis by the gel in the shrunken state is well described by the Michaelis-Menten formula, indicating that the absorption of the substrate by the hydrophobic environment created by the N-isopropylacrylamide polymer in the shrunken gel is responsible for enhancement of catalytic activity. In the swollen state, the rate vs. active site concentration is linear, indicating that the substrate absorption is not a primary factor determining the kinetics. Catalytic activity of the gel is studied for substrates with various alkyl chain lengths; of those studied the switching effect is most pronounced for p-nitrophenyl caprylate.
authors.affiliation: Department of Physics and Center for Materials Science and Engineering, and Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, MA 02139, USA.
authors.forename: G
authors.initials: G
authors.lastname: Wang
authors.forename: K
authors.initials: K
authors.lastname: Kuroda
authors.forename: T
authors.initials: T
authors.lastname: Enoki
authors.forename: A
authors.initials: A
authors.lastname: Grosberg
authors.forename: S
authors.initials: S
authors.lastname: Masamune
authors.forename: T
authors.initials: T
authors.lastname: Oya
authors.forename: Y
authors.initials: Y
authors.lastname: Takeoka
authors.forename: T
authors.initials: T
authors.lastname: Tanaka
mesh_terms: D000178:Acrylamides; D002210:Caprylates / Q000737:chemistry*; D002384:Catalysis; D000431:Ethanol; D005782:Gels; D006868:Hydrolysis; D007700:Kinetics; D012997:Solvents; D014867:Water
chemical_list: D000178:Acrylamides; D002210:Caprylates; D005782:Gels; D012997:Solvents; D014867:Water; C034106:4-nitrophenyloctanoate; D000431:Ethanol; C067295:N-isopropylacrylamide