Synthesis of the Polysaccharide, (1→5)- α-D-Ribofuranan and Its Catalytic Activities for the Hydrolysis of Phosphates and the Cleavage of Nucleic Acids

Man Jung Han; Kyung Soo Yoo; Young Heui Kim; Hong Youb Kim; Hyun Joon Shin; Ji Young Chang

Macromolecular Research, Vol.12, No.4, 359-366, August, 2004

Man Jung Han^†, Kyung Soo Yoo, Young Heui Kim, Hong Youb Kim, Hyun Joon Shin, and Ji Young Chang¹

Department of Molecular Science and Technology, Ajou University, Suwon 442-749, Korea
¹School of Materials Science and Engineering, and Hyperstructured Organic Materials Research Center, Seoul National University, Seoul 151-744, Korea

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The polysaccharide, (1→5)- α-D-ribofuranan, was synthesized by a cationic ring-opening polymerization of 1,4-anhydro-2,3-di-O-benzyl-α-D-ribopyranose with the aid of boron trifluoride etherate and subsequent debenzylation. This polysaccharide catalyzed the hydrolysis of ethyl p-nitrophenyl phosphate, uridylyl(3´→5´)uridine ammonium salt, and 4-tert-butylcatechol cyclic phosphate N-methyl pyridinium. The polymer also catalyzed the cleavage of nucleic acids (DNA and RNA). The hydrolysis of ethyl p-nitrophenyl phosphate in the presence of the polymer was accelerated by 1.5×10³ times relative to the uncatalyzed reaction. The catalytic activity was attributable to the vic-cis-diols of the riboses being located inside the active center that is formed by polymer chain folding; these diols form hydrogen bonds with two phosphoryl oxygen atoms of the phosphates so as to activate the phosphorus atoms to be attacked by nucleophile (H₂O).

Keywords:polysaccharide;catalytic activity;ribose;nucleic acid

[References]

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Han MJ, Yoo KS, Cho TJ, Chang JY, Cha YJ, Nam SH, Chem. Commun., 163 (1997)
Han MJ, Yoo KS, Kim KH, Lee GH, Chang JY, Macromolecules, 30(18), 5408 (1997)
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Uryu T, Yamanouchi J, Kato T, Higuchi S, Matsuzaki K, J. Am. Chem. Soc., 105, 6865 (1983)
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Ha TK, Suleimenov OM, Han MJ, Theochem-J. Mol. Struct., 574, 75 (2001)
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[Related Articles]

[1] Kunitake T, Okahata Y, Adv. Polym. Sci., 20, 159 (1976)

[2] Kunitake T, in Polymer-supported Reactions in Organic Synthesis, P. Hodge and D. D. Sherrington, Eds., John Wiley & Sons, New York, 195 (1980)

[3] Overberger CG, Pierre TSt, Vorchheimer N, Yaroslavsky S, J. Am. Chem. Soc., 85, 3513 (1963)

[4] Overberger CG, Okamoto Y, Macromolecules, 5, 363 (1972)

[5] Guerrier-Takada C, Altman S, Science, 223, 285 (1983)

[6] Breaker RR, Joyce GF, Chem. Biol., 1, 223 (1994)

[7] Breslow R, Doherty JB, Buillot G, Lipsey C, J. Am. Chem. Soc., 100, 3227 (1978)

[8] Breslow R, Bovy P, Hersh CL, J. Am. Chem. Soc., 102, 2115 (1980)

[9] Han MJ, Yoo KS, Chang JY, Ha TK, Angew. Chem.-Int. Edit., 39, 347 (2000)

[10] Han MJ, Yoo KS, Cho TJ, Chang JY, Cha YJ, Nam SH, Chem. Commun., 163 (1997)

[11] Han MJ, Yoo KS, Kim KH, Lee GH, Chang JY, Macromolecules, 30(18), 5408 (1997)

[12] Khwaja TA, Resse CB, Stewart JCM, J. Chem. Soc., 2092 (1970)

[13] Uryu T, Yamanouchi J, Kato T, Higuchi S, Matsuzaki K, J. Am. Chem. Soc., 105, 6865 (1983)

[14] Uryu T, Kitano K, Ito K, Yamanouchi J, Matsuzaki K, Macromolecules, 14, 1 (1981)

[15] Ha TK, Suleimenov OM, Han MJ, Theochem-J. Mol. Struct., 574, 75 (2001)

[16] Sugimura T, Fujimura S, Hasegawa S, Kawamura Y, Biochim. Biophys. Acta, 138, 438 (1967)

[17] Ueda K, Hayaishi O, Ann. Rev. Biochem., 54, 73 (1985)

[18] Lautier D, Lagueus J, Thibodeau J, Mennard L, Poirier GG, Mol. Cell. Biochem., 122, 171 (1993)

[19] Alvarez-Gonzalez R, Pacheco-Rodriguez G, Men-doza-Alvarez H, Mol. Cell. Biochem., 138, 33 (1994)

[20] Maruta H, Matsumura N, Tanuma S, Biochem. Biophys. Res. Commun., 236, 265 (1997)

[21] Satoh MS, Poirier GG, Lindahl T, Biochemistry, 33, 7099 (1994)

[22] Simbulan-Rosenthal CM, Rosenthal DS, Lyer S, Boulares AH, Smulson ME, J. Biol. Chem., 273, 13703 (1998)

[23] Malanga M, Althaus FR, J. Biol. Chem., 269, 17691 (1994)

[24] Satoh MS, Poirier GG, Lindahl T, Biochemistry, 33, 7099 (1994)