Abstract
A well-defined poly(ethylene glycol) (PEG) possessing a 2-pyridyldithio end group at one end and a carboxyl group at the other end was prepared after chemical modification of the α-allyl-ω-carboxyl PEG, which was synthesized by an anionic ring-opening polymerization of ethylene oxide (EO) using potassium allyl alcoholate as the initiator, followed by the modification of the ω-end-alkoxide group to a carboxyl group using succinic anhydride. The allyl end group was modified by the radical addition reaction of thioacetic acid in the presence of azoisobutyronitrile (AIBN) that led to α-thioacetate-ω-carboxyl PEG without any side reaction. Selective hydrolysis of the thioester end group was accomplished by n-alkylamine in the presence of 2,2′-dithio pyridine (2-PDS) to give α-pyridyldithio-ω-carboxyl PEG with no aminolysis to the oxoester of the carboxyl group of the other end. The functionalities of both ends characterized by NMR spectra, were almost quantitative.
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Y. Mori, S. Nagaoka, H. Takiuchi, T. Kikuchi, N. Noguchi, H. Tanzawa, and Y. Noishiki, Trans. Am. Soc. Artif. Intern. Organs, 28, 459 (1982).
J. M. Harris, M. R. Sedaghat-Herati, P. J. Sather, D. E. Brooks, and T. M. Fyles, in “Poly(ethylene glycol) Chemistry: Biotechnical and Biomedical Applications,” J. M. Harris, Ed., Plenum Press, New York, N.Y., 1992.
F. E., Jr. Bailey and J. V. Koleske, Ed., “Alkylene Oxide and Their Polymers, Vol. 35,” Marcel Dekker, New York, N.Y., 1991.
F. Fuertges and A. Abuchowski, J. Controlled Release, 11, 139 (1990).
Y. K. Park, A. Abuchowski, S. Davis, and F. Davis, Anticancer Res., 1, 373 (1981).
R. Ramachandran, D. Katzenstein, M. A. Winters, S. K. Kundu, and T. C. Merigan, J. Infect. Dis., 173, 1005 (1996).
K. Kataoka, A. Harada, and Y. Nagasaki, Adv. Drug Delivery Rev., 47, 113 (2001).
Y. Deguchi, A. Kurihara, and W. M. Pardridge, Bioconjugate Chem., 10, 32 (1999).
R. B. Greenwald, K. Yang, H. Zhao, C. D. Conover, S. Lee, and D. Filpula, Bioconjugate Chem., 14, 395 (2003).
H. Otsuka, Y. Nagasaki, and Kataoka, Curr. Opin. Colloid Interface Sci., 6, 3 (2001).
A. Kurihara and W. M. Pardridge, Bioconjugate Chem., 11, 380 (2000).
E. C. Unger, D. Shen, G. Wu, L. Stewart, T. O. Matsunaga, and T. P. Trouard, Magn. Reson. Mater. Phys., Biol. Med., 8, 154 (1999).
V. P. Torchilin, Colloids Surf. B., 16, 305 (1999).
J. D. Andrade, V. Hlady, and S.-I. Jeon, in “Hydrophilic Polymers: Poly(ethylene oxide) and Protein Resistance,” J. E. Glass, Ed., American Chemical Society, Washington, D.C., 1996, p. 51.
M. Hasan, D. Bethell, and M. Brust, J. Am. Chem. Soc., 124, 1132 (2002).
H. Otsuka, Y. Akiyama, Y. Nagasaki, and K. Kataoka, J. Am. Chem. Soc., 47, 8226 (2001).
W. P. Wuelfing, S. M. Grass, D. T. Miles, and R. W. Murray, J. Am. Chem. Soc., 120, 12696 (1998).
Y. Nagasaki, T. Kutsuna, M. Iijima, M. Kato, K. Kataoka, S. Kitano, and Y. Kodama, Bioconjugate Chem., 6, 231 (1995).
T. Nakamura, Y. Nagasaki, M. Kato, and K. Kataoka, in “Biomedical Engineering and Drug Delivery System: Synthesis of Heterobifunctional Poly(ethylene glycol) with a Reducing Monosaccharide Residue at One End for Drug Delivery, Systems,” N. Ogata, S. W. Kim, J. Fijen, and T. Okano, Ed., Springer, Tokyo, 1996.
Y. Nagasaki, M. Iijima, M. Kato, and K. Kataoka, Bioconjugate Chem., 6, 702 (1995).
S. Cammas, Y. Nagasaki, and K. Kataoka, Bioconjugate Chem., 6, 226 (1995).
Y. Akiyama, Y. Nagasaki, and K. Kataoka, Bioconjugate Chem., 15, 424 (2004).
M. Oishi, T. Tsuruta, K. Kataoka, and Y. Nagasaki, to be submitted.
Y. Akiyama, H. Otsuka, Y. Nagasaki, M. Kato, and K. Kataoka, Bioconjugate Chem., 11, 947 (2000).
K. Uchida, H. Otsuka, Y. Nagasaki, and K. Kataoka, to be submitted.
O. Rheingans, N. Hugenberg, J. R. Harris, K. Fischer, and M. Maskos, Macromolecules, 33, 4780 (2000).
H. Hayashi, M. Iijima, K. Kataoka, and Y. Nagasaki, Macromolecules, 37, 5389 (2004).
C. M. Starks, “Free Radical Telomerization,” Academic Press, New York, N.Y., 1974.
S. Herrwerth, T. Rosendahl, C. Feng, J. Fick, W. Eck, M. Himmelhaus, R. Dahint, and M. Grunze, Langmuir, 19, 1880 (2003).
T. W. Green and P. G. M. Wuts, “Protective Groups in Organic Synthesis, 3rd ed.,” John Wiley & Sons, New York, N.Y., 1999.
W. Yang and D. G. Drueckhammer, J. Am. Chem. Soc., 123, 11004 (2001).
T. Uete, Y. Miyamoto, M. Ohnishi, and N. Shimano, Clin. Chem., 18, 454 (1972).
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Ishii, T., Yamada, M., Hirase, T. et al. New Synthesis of Heterobifunctional Poly(ethylene glycol) Possessing a Pyridyl Disulfide at One End and a Carboxylic Acid at the Other End. Polym J 37, 221–228 (2005). https://doi.org/10.1295/polymj.37.221
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DOI: https://doi.org/10.1295/polymj.37.221
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