Molecularly Imprinted Polymers Having Amidine and Imidazole Functional Groups As an Enzyme-Mimetic Catalyst for Ester Hydrolysis

Wen Chen; Dong-Keun Han; Kwang-Duk Ahn; Jong-Man Kim

Macromolecular Research, Vol.10, No.2, 122-126, April, 2002

Wen Chen, Dong-Keun Han , Kwang-Duk Ahn^†, and Jong-Man Kim¹

Functional Polymer Laboratory, Korea Institute of Science and Technology, P.O. Box 131, Cheongryang, Seoul 130-650, Korea
¹College of Engineering, Hanyang University, Seongdong-Ku, Seoul 133-791, Korea

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A molecularly imprinted polymer (MIP) having both amidine and imidazole functional groups in the active site has been prepared using p-nitrophenyl phosphate as a transition state analogue (TSA). The imprinted polymer MIP with amidine and imidazole found to have the highest hydrolysis activity compared with other MIPs with either amidine or imidazole groups only. It is postulated a cooperative effect between amidine and imidazole in the hydrolysis of p-nitrophenyl methyl carbonate (NPMC) as a substrate when both groups were arranged in proximity by molecular imprinting. The rate enhancement of the hydrolysis by MIP was 60 folds over the uncatalyzed solution reaction and two folds compared with the control non-imprinted polymer CP1 having both functional groups. The enzyme-mimetic catalytic hydrolysis of p-nitrophenyl acetate by MIP was evaluated in buffer at pH 7.0 with Km of 1.06 mM and kcat of 0.137 h(-1).

Keywords:molecularly imprinted polymers;molecularly imprinting catalysts;enzyme-mimetic reaction;amidine functional;imidazole functional;transition state analogue imprinting

[References]

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Wulff G, Chemtech., 19, 19 (1998)
Kim JM, Ahn KD, Polym. Sci. Technol., 9(2), 137 (1998)
Ahn KD, Kim JM, Polym. Sci. Technol., 11(3), 332 (2000)
Dicker FL, Hayden O, Adv. Mater., 12, 311 (2000)
Piletsky S, Alcock S, Turner ARF, Trends Biotechnol., 19, 9 (2001)
Sellergren B, Angew. Chem.-Int. Edit., 39, 1031 (2000)
Whitcomb M, Vulfson EN, Adv. Mater., 13, 467 (2000)
Asansuma H, Hishiya T, Komiyama M, Adv. Mater., 12, 1019 (2000)
Kugimiya A, Kuwada Y, Takeuchi T, J. Chromatogr. A, 938, 131 (2001)
Kriz O, Ramstrom O, Mosbach K, Anal. Chem., 69, 345A (1997)
Lerner RA, Benkvoic SJ, Schultz PG, Science, 252, 659 (1991)
Leonhardt A, Mosbach K, React. Polym., 6, 285 (1987)
Robinson DK, Mosbach K, J. Chem. Soc.-Chem. Commun., 969 (1989)
Ohkubo K, Urata Y, Hirota S, Honda Y, Fujishita Y, Sagawa T, J. Mol. Catal., 87, L21 (1994)
Beach JV, Shea KJ, J. Am. Chem. Soc., 116(1), 379 (1994)
Sellergren B, Karmalkar RN, Shea KJ, J. Org. Chem., 65, 4009 (2000)
Kim JM, Ahn KD, Wulff G, Macromol. Chem. Phys., 202, 1105 (2001)
Strikovsky AG, Kasper D, Grun M, Green BS, Hradil J, Wulff G, J. Am. Chem. Soc., 122(26), 6295 (2000)
Wulff G, Gross T, Schonfeld R, Angew. Chem.-Int. Edit., 36, 1962 (1997)
Kim JM, Ahn KD, Strikovsky G, Wulff G, Bull. Korean Chem. Soc., 22, 689 (2001)
Wulff G, Schonfeld R, Adv. Mater., 10, 957 (1998)
Overberger CG, Pierre T, Vorchheimer N, Lee J, Yaroslavsky S, J. Am. Chem. Soc., 87, 296 (1969)
Lele BS, Kulkarni MG, Mashelkar RA, React. Funct. Polym., 39(1), 37 (1999)
Dugas H, Bioorganic Chemistry, Third Ed., Springer-Verlag, New York, U.S.A., pp. 192 (1996)

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[1] Wulff G, Chem. Rev., 102(1), 1 (2002)

[2] Wulff G, Angew. Chem.-Int. Edit., 34, 1812 (1995)

[3] Wulff G, Chemtech., 19, 19 (1998)

[4] Kim JM, Ahn KD, Polym. Sci. Technol., 9(2), 137 (1998)

[5] Ahn KD, Kim JM, Polym. Sci. Technol., 11(3), 332 (2000)

[6] Dicker FL, Hayden O, Adv. Mater., 12, 311 (2000)

[7] Piletsky S, Alcock S, Turner ARF, Trends Biotechnol., 19, 9 (2001)

[8] Sellergren B, Angew. Chem.-Int. Edit., 39, 1031 (2000)

[9] Whitcomb M, Vulfson EN, Adv. Mater., 13, 467 (2000)

[10] Asansuma H, Hishiya T, Komiyama M, Adv. Mater., 12, 1019 (2000)

[11] Kugimiya A, Kuwada Y, Takeuchi T, J. Chromatogr. A, 938, 131 (2001)

[12] Kriz O, Ramstrom O, Mosbach K, Anal. Chem., 69, 345A (1997)

[13] Lerner RA, Benkvoic SJ, Schultz PG, Science, 252, 659 (1991)

[14] Leonhardt A, Mosbach K, React. Polym., 6, 285 (1987)

[15] Robinson DK, Mosbach K, J. Chem. Soc.-Chem. Commun., 969 (1989)

[16] Ohkubo K, Urata Y, Hirota S, Honda Y, Fujishita Y, Sagawa T, J. Mol. Catal., 87, L21 (1994)

[17] Beach JV, Shea KJ, J. Am. Chem. Soc., 116(1), 379 (1994)

[18] Sellergren B, Karmalkar RN, Shea KJ, J. Org. Chem., 65, 4009 (2000)

[19] Kim JM, Ahn KD, Wulff G, Macromol. Chem. Phys., 202, 1105 (2001)

[20] Strikovsky AG, Kasper D, Grun M, Green BS, Hradil J, Wulff G, J. Am. Chem. Soc., 122(26), 6295 (2000)

[21] Wulff G, Gross T, Schonfeld R, Angew. Chem.-Int. Edit., 36, 1962 (1997)

[22] Kim JM, Ahn KD, Strikovsky G, Wulff G, Bull. Korean Chem. Soc., 22, 689 (2001)

[23] Wulff G, Schonfeld R, Adv. Mater., 10, 957 (1998)

[24] Overberger CG, Pierre T, Vorchheimer N, Lee J, Yaroslavsky S, J. Am. Chem. Soc., 87, 296 (1969)

[25] Lele BS, Kulkarni MG, Mashelkar RA, React. Funct. Polym., 39(1), 37 (1999)

[26] Dugas H, Bioorganic Chemistry, Third Ed., Springer-Verlag, New York, U.S.A., pp. 192 (1996)