가교 폴리(4-비닐피리딘)-구리(II) 착물에 의한 Ascorbic Acid의 산화반응

김우식; 이석기; 남기영; 구광모; 이길준; 박병각

Polymer(Korea), Vol.22, No.6, 1020-1026, November, 1998

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가교 폴리(4-비닐피리딘)-구리(II) 착물에 의한 Ascorbic Acid의 산화반응

Oxidation of Ascorbic Acid by Crosslinked Poly(4-vinylpyridine)-Cu(II) Complexes

김우식, 이석기, 남기영, 구광모, 이길준, 박병각

초록

4-비닐피리딘과 N,N''-메틸렌비스아크릴아미드를 라디칼 공중합하여 여러가지 가교도를 가지는 가교 폴리(4-비닐피리딘)(CP4VP)을 제조하였고, 이들 가교 고분자와 구리(II)와의 착물의 안정화상수를 평형흡착법으로 측정하였다. 또 이 착물들을 ascorbic acid(AA) 산화반응에 사용하여 촉매활성을 조사하였다. CP4VP-Cu(II) 착물의 안정화상수는 가교도가 증가할수록 감소하였다. CP4VP-Cu(II) 착물은 CP4VP의 가교도가 증가할수록 산화반응의 촉매활성이 증가하였다. 이들 결과는 CP4VP의 가교도가 AA 산화반응의 촉매활성에 중요한 요인이 된다는 것을 의미한다. 그리고 CP4VP-Cu(II) 착물에 의한 AA 산화반응은 Michaelis-Menten형 속도론적 거동을 나타내었다.

The crosslinked poly(4-vinylpyridines) (CP4VP) having different degrees of crosslinking were prepared by radical copolymerization of 4-vinylpyridine with N,N''-methylenebisacrylamide. The stability constants of CP4VP-Copper(II) complexes were measured by the method of adsorption equilibrium, and the catalytic activities of the complexes for the oxidation of ascorbic acid (AA) were also measured. The stability constants of CP4VP-Cu (II) complexes were decreased with the increase of the degree of crosslinking. The catalytic activities of CP4VP-Cu(II) complexes were increased with the increase of the degree of crosslinking of CP4VP. These results indicate that the degree of crosslinking is an important factor in the catalytic activity of the oxidation of AA. In addition, the oxidation of AA by these complexes showed the kinetic behavior of the Michaelis-Menten type.

Keywords:crosslinked poly(4-vinylpyridine);complex stability constant;degree of crosslinking;ascorbic acid;catalytic activity

[References]

Skurlatov YI, Kovner VY, Travin SO, Kirsh YE, Purmal AP, Kabanov VA, Eur. Polym. J., 15, 811 (1979)
Tsuchida E, Niside H, Nishiyama T, J. Polym. Sci. C: Polym. Lett., 47, 35 (1974)
Tsuchida E, Kaneko M, Niside H, Macromol. Chem., 174, 203 (1973)
Breslow R, McCure DE, Brown RS, Eisennach J, J. Am. Chem. Soc., 97, 194 (1975)
Gebelein CG, Charraher CE, "Bioactive Polymeric Systems," Plenum Press, New York (1985)
Saegusa T, Hirai H, Tsuchida E, "Polymer-Metal Complexes," Kagaku Do-Jin, Kyoto (1978)
Takemoto K, Inaki Y, Ottenbrite RM, "Functional Monomers and Polymers," Marcel Dekker Inc., New York (1987)
Pecht I, Levitzki A, Anbar M, J. Am. Chem. Soc., 89, 1587 (1967)
Yamashita K, Okada I, Suzuki Y, Tsuda K, Makromol. Chem. Rapid Commun., 9, 705 (1988)
Yamashita K, Kanamori T, Nagano M, Tsuda K, Polymer, 34, 2638 (1993)
Egawa H, Nonaka T, Kozakura N, Bull. Chem. Soc. Jpn., 55, 3536 (1982)
Lee SK, Park NK, Kim WS, J. Korean Ind. Eng. Chem., 1(2), 182 (1990)
Niside H, Tsuchida E, Makromol. Chem., 177, 2295 (1976)
Niside H, Deguchi J, Tsuchida E, Bull. Chem. Soc. Jpn., 49, 3498 (1976)
Agnew NH, J. Polym. Sci. A: Polym. Chem., 14, 2819 (1976)
Lineweaver H, Burk D, J. Am. Chem. Soc., 56, 658 (1934)
Lee SK, Seo KH, Kim WS, Polymer, 34, 2392 (1993)
Kim WS, Lee SK, Seo KH, Macromol. Chem. Phys., 195, 449 (1994)

[Referenced By]

[1] Skurlatov YI, Kovner VY, Travin SO, Kirsh YE, Purmal AP, Kabanov VA, Eur. Polym. J., 15, 811 (1979)

[2] Tsuchida E, Niside H, Nishiyama T, J. Polym. Sci. C: Polym. Lett., 47, 35 (1974)

[3] Tsuchida E, Kaneko M, Niside H, Macromol. Chem., 174, 203 (1973)

[4] Breslow R, McCure DE, Brown RS, Eisennach J, J. Am. Chem. Soc., 97, 194 (1975)

[5] Gebelein CG, Charraher CE, "Bioactive Polymeric Systems," Plenum Press, New York (1985)

[6] Saegusa T, Hirai H, Tsuchida E, "Polymer-Metal Complexes," Kagaku Do-Jin, Kyoto (1978)

[7] Takemoto K, Inaki Y, Ottenbrite RM, "Functional Monomers and Polymers," Marcel Dekker Inc., New York (1987)

[8] Pecht I, Levitzki A, Anbar M, J. Am. Chem. Soc., 89, 1587 (1967)

[9] Yamashita K, Okada I, Suzuki Y, Tsuda K, Makromol. Chem. Rapid Commun., 9, 705 (1988)

[10] Yamashita K, Kanamori T, Nagano M, Tsuda K, Polymer, 34, 2638 (1993)

[11] Egawa H, Nonaka T, Kozakura N, Bull. Chem. Soc. Jpn., 55, 3536 (1982)

[12] Lee SK, Park NK, Kim WS, J. Korean Ind. Eng. Chem., 1(2), 182 (1990)

[13] Niside H, Tsuchida E, Makromol. Chem., 177, 2295 (1976)

[14] Niside H, Deguchi J, Tsuchida E, Bull. Chem. Soc. Jpn., 49, 3498 (1976)

[15] Agnew NH, J. Polym. Sci. A: Polym. Chem., 14, 2819 (1976)

[16] Lineweaver H, Burk D, J. Am. Chem. Soc., 56, 658 (1934)

[17] Lee SK, Seo KH, Kim WS, Polymer, 34, 2392 (1993)

[18] Kim WS, Lee SK, Seo KH, Macromol. Chem. Phys., 195, 449 (1994)