Synthesis and pH-Dependent Micellization of a Novel Block Copolymer Containing s-Triazine Linkage

Ravindra R. Pal; Doo Sung Lee

Macromolecular Research, Vol.13, No.5, 373-384, October, 2005

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Synthesis and pH-Dependent Micellization of a Novel Block Copolymer Containing s-Triazine Linkage

Ravindra R. Pal, and Doo Sung Lee^†

Department of Polymer Science and Engineering, Sungkyunkwan University, Suwon, Gyeonggi 440-746, Korea

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Novel pH-sensitive moieties containing an s-triazine ring were synthesized with sulfonamide and secondary amino groups. The synthesized pH-sensitive moieties were used for the synthesis of a pH-sensitive amphiphilic ABA triblock copolymer. The pH-sensitive triblock copolymer was composed of diblock copolymers, methoxy poly(ethylene glycol)-poly ( ε-caprolactone-co-D,L-lactide) (MPEG-PCLA), and pH-sensitive moiety. These copolymers could be dissolved molecularly in both acidic and basic aqueous media at room temperature due to secondary amino and sulfonamide groups. The synthesized s-triazine rings containing pH-sensitive compounds were characterized by 1H-NMR, 13C-NMR, and LC/MSD spectral data. The synthesized diblock and triblock copolymers were also characterized by 1H-NMR and GPC analyses. The critical micelle concentrations at various pH conditions were determined by fluorescence technique using pyrene as a probe. Furthermore, the micellization and demicellization study of the triblock copolymer was done with pH-sensitive groups. The sensitivity towards pH change was further established by acid-base titration.

Keywords:ABA triblock copolymers;s-triazine ring;pH-sensitive moiety;critical micelle concentration;micellization/demicellization

[References]

Uhrich KE, Cannizzaro SM, Langer RS, Shakesheff KM, Chem. Rev., 99(11), 3181 (1999)
Jain RK, J. Control. Release, 53, 49 (1998)
Au JLS, Jang SH, Zheng J, Chen CT, Song S, Hu L, Weintjes MG, J. Control. Release, 74, 31 (2001)
Liu XM, Wang LS, Biomaterials, 25, 1929 (2004)
Potineni A, Lynn DM, Langer R, Amiji MM, J. Control. Release, 86, 223 (2003)
Han SK, Na K, Bae YH, Colloids Surf. A: Physicochem. Eng. Asp., 49, 214 (2003)
Ono M, Kawahara N, Goto D, Wakahayashi Y, Ushiro S, Yoshida S, Izumi H, Kuwano M, Sato Y, Cancer Res., 56, 1512 (1996)
Draber W, Tietjin K, Kluth JF, Trebst A, Angew. Chem.-Int. Edit., 30, 1621 (1991)
Hajduk PJ, Dinges J, Schkeryantz JM, Janowick D, Kaminski M, Tufano M, Auri DJ, Petros A, Nienaber V, Zhong P, Hammond R, Coen M, Beutel B, Katz L, Fesik SW, J. Med. Chem., 42, 3842 (1999)
Maeda M, Iigo M, Tsuda H, Fujita H, Yonemura Y, Nakagawa K, Endo Y, Sasaki T, Anti-Cancer Drugs Res., 15, 217 (2000)
Pal RR, Patil PS, Salunkhe MM, Maldar NN, Wadgaonkar PP, Polym. Int., 54, 569 (2005)
Sagar AD, Shingte RD, Wadgaonkar PP, Salunkhe MM, Eur. Polym. J., 37, 1493 (2001)
Irles N, Pauiggali J, Subirana JA, Macromol. Chem. Phys., 202, 3316 (2001)
Klenke B, Stewart M, Barrett MP, Brun R, Gilbert IH, J. Med. Chem., 44, 3440 (2001)
Allen RLM, Color Chemistry, Appleton-century-crofts, New York (1971)
Adam MJ, Hall LD, Carbohydr. Res., 144, 23 (1985)
Ono K, Kai Y, Maeda H, Samizo F, Sakurai K, Nishimura H, Inada Y, J. Biomater. Sci.-Polym. Ed., 2, 61 (1991)
Khersonsky SM, Jung DW, Kang TW, Walsh DP, Moon HS, Jo H, Jacobson EM, Shetty V, Neubert TA, Chang YT, J. Am. Chem. Soc., 125(39), 11804 (2003)
Samolin EM, Rapport L, Chem. Heterocycl. Compd., 13 (1959)
Scharn D, Reineke U, Schneider-Mergener J, Germeroth J, Comm. Chem., 2, 361 (2000)
Johnson CR, Zhang B, Fantauzzi P, Hocker M, Yager KM, Tetrahedron, 54, 4097 (1998)
de Hoog P, Gamez P, Driessen WL, Reedijk J, Tetrahedron Lett., 43, 6783 (2002)
Jones TJ, Brasseur N, Lier Van JE, Leroux JC, J. Pharm. Sci., 89, 52 (2000)
Moore JS, Stupp SI, Macromolecules, 23, 65 (1990)
Kloetzer W, Mon. Chem., 93, 1055 (1962)

[Referenced By]

[Related Articles]

[1] Uhrich KE, Cannizzaro SM, Langer RS, Shakesheff KM, Chem. Rev., 99(11), 3181 (1999)

[2] Jain RK, J. Control. Release, 53, 49 (1998)

[3] Au JLS, Jang SH, Zheng J, Chen CT, Song S, Hu L, Weintjes MG, J. Control. Release, 74, 31 (2001)

[4] Liu XM, Wang LS, Biomaterials, 25, 1929 (2004)

[5] Potineni A, Lynn DM, Langer R, Amiji MM, J. Control. Release, 86, 223 (2003)

[6] Han SK, Na K, Bae YH, Colloids Surf. A: Physicochem. Eng. Asp., 49, 214 (2003)

[7] Ono M, Kawahara N, Goto D, Wakahayashi Y, Ushiro S, Yoshida S, Izumi H, Kuwano M, Sato Y, Cancer Res., 56, 1512 (1996)

[8] Draber W, Tietjin K, Kluth JF, Trebst A, Angew. Chem.-Int. Edit., 30, 1621 (1991)

[9] Hajduk PJ, Dinges J, Schkeryantz JM, Janowick D, Kaminski M, Tufano M, Auri DJ, Petros A, Nienaber V, Zhong P, Hammond R, Coen M, Beutel B, Katz L, Fesik SW, J. Med. Chem., 42, 3842 (1999)

[10] Maeda M, Iigo M, Tsuda H, Fujita H, Yonemura Y, Nakagawa K, Endo Y, Sasaki T, Anti-Cancer Drugs Res., 15, 217 (2000)

[11] Pal RR, Patil PS, Salunkhe MM, Maldar NN, Wadgaonkar PP, Polym. Int., 54, 569 (2005)

[12] Sagar AD, Shingte RD, Wadgaonkar PP, Salunkhe MM, Eur. Polym. J., 37, 1493 (2001)

[13] Irles N, Pauiggali J, Subirana JA, Macromol. Chem. Phys., 202, 3316 (2001)

[14] Klenke B, Stewart M, Barrett MP, Brun R, Gilbert IH, J. Med. Chem., 44, 3440 (2001)

[15] Allen RLM, Color Chemistry, Appleton-century-crofts, New York (1971)

[16] Adam MJ, Hall LD, Carbohydr. Res., 144, 23 (1985)

[17] Ono K, Kai Y, Maeda H, Samizo F, Sakurai K, Nishimura H, Inada Y, J. Biomater. Sci.-Polym. Ed., 2, 61 (1991)

[18] Khersonsky SM, Jung DW, Kang TW, Walsh DP, Moon HS, Jo H, Jacobson EM, Shetty V, Neubert TA, Chang YT, J. Am. Chem. Soc., 125(39), 11804 (2003)

[19] Samolin EM, Rapport L, Chem. Heterocycl. Compd., 13 (1959)

[20] Scharn D, Reineke U, Schneider-Mergener J, Germeroth J, Comm. Chem., 2, 361 (2000)

[21] Johnson CR, Zhang B, Fantauzzi P, Hocker M, Yager KM, Tetrahedron, 54, 4097 (1998)

[22] de Hoog P, Gamez P, Driessen WL, Reedijk J, Tetrahedron Lett., 43, 6783 (2002)

[23] Jones TJ, Brasseur N, Lier Van JE, Leroux JC, J. Pharm. Sci., 89, 52 (2000)

[24] Moore JS, Stupp SI, Macromolecules, 23, 65 (1990)

[25] Kloetzer W, Mon. Chem., 93, 1055 (1962)