Poly(γ-methyl L-glutamate)/Poly (propylene oxide)/Poly(γ-methyl L-glutamate) 블록 공중합체의 합성, 구조연구 및 혈액 적합성

조종수; 김희용; 송수창; 양동욱; 김주오; 김상수

Polymer(Korea), Vol.15, No.1, 49-56, February, 1991

Synthesis, Structural Studies of ABA Triblock Copolymers Composed of Poly(γ-methyl L-glutamate) as the A Component and Poly(propylene oxide) as the B Component and Their Blood Compatibility

조종수, 김희용, 송수창, 양동욱, 김주오, 김상수

초록

poly(γ-methyl L-glutamate) (PMLG)를 A성분으로 하고 poly(propylene oxide) (PPO)를 B성분으로 구성된 ABA형 블록 공중합체가 poly(propylene oxide)의 양 말단에 있는 아미노기를 개시제로 γ-MLG NCA가 개환되는 친핵성첨가 mechanism에 의해 합성되었다. Trifluoroethanol 용액에서의 원이색성(CD)측정과 고체상에서의 IR측정으로부터 이 블록공중합체가 PMLG homopolymer와 같이 전형적인 α-helix구조를 가지고 있음을 알았다. 이 블록공중합체 표면에서의 혈소판 흡착실험은 platelet-rich plasma(PRP)를 사용하여 depositing 방법으로 행하였고, 혈소판의 흡착정도는 블록공중합체의 poly(propylene oxide)의 함량에 의존함을 알았다.

ABA type triblock copolymers consisting of poly(γ-methyl L-glutamate) (PMLG) as outer blocks and poly(propylene oxide) (PPO) as the middle block were synthesized by polymerization of γ-methyl L-glutamate N-carboxyanhydride by amine terminated poly(propylene oxide). in which the terminal amine groups act as an initiator. From circular dichroism measurements of the block copolymer in trifluoroethanol solution as well as from infrared spectra in the solid state, it was found that the polypeptide block exists in the α-helical conformation, as in the PMLG homopolymer. Platelets adhesion on the block copolymer surfaces was examined by depositing method using platelet-rich plasma(PRP). This result shows that platelet adhesion on the PMLG/PPO block copolymer surface was dependant on the content of PPO in the block copolymer.

[References]

Sakurai Y, Akaike T, Kataoka K, Okano T, "Interfacial Phenomena in Biomaterial Chemistry," A. Nakajima and E. Goldberg, Eds., Academic, New York, pp. 335-379 (1980)
Andrade JD, Med. Instrum., 7, 110 (1973)
Okano T, Nishiyama S, Shinohara I, Akaike T, Sakurai Y, Kataoka K, Tsuruta T, Kuwana K, Miyata S, Artificial Org., 3, 253 (1979)
Kim SW, Ebert CD, Lin JY, Mcrea JC, ASAIO J., 6, 76 (1983)
Heyman PW, Cho CS, McRea JC, Olsen DW, Kim SW, J. Biomed. Mater. Res., 19, 419 (1985)
Lyman DJ, Hill DW, Stirk RK, Adamson C, Mooney BR, Trans. Am. Soc. Artif. Intern. Org., 18, 19 (1972)
Okano T, Nishiyama S, Shinohara I, Akaike T, Sakurai Y, Kataoka K, Tsuruta T, J. Biomed. Mater. Res., 15, 393 (1981)
Sawyer PN, Burrowes C, Ogoniak J, Smith AO, Wesolowski SA, Trans. Am. Soc. Artif. Intern. Organs., 10, 316 (1964)
Nakajima A, Hayashi T, Kugo K, Shinoda K, Macromolecules, 12, 840 (1979)
Nakajima A, Kugo K, Hayashi T, Macromolecules, 12, 844 (1979)
Nakajima A, Kugo K, Hayashi T, Polym. J., 11, 995 (1979)
Chen GW, Hayashi T, Nakajima A, Polym. J., 13, 433 (1981)
Kugo K, Hayashi T, Nakajima A, Polym. J., 14, 401 (1982)
Kugo K, Murashima M, Hayashi T, Nakajima A, Polym. J., 15, 267 (1983)
Okano T, Uruno M, Sugiyama N, Shimada M, Shinohara I, Kataoka K, Sakurai Y, J. Biomed. Mater. Res., 20, 1035 (1986)
Nishimura T, Sato Y, Yokoyama M, Okuya M, Inoue S, Kataoka K, Okano T, Sakurai Y, Makromol. Chem., 185, 2079 (1984)
Cho CS, Kim SW, Sung YK, Kim KY, Makromol. Chem., 189, 1505 (1988)
Cho CS, Song SC, Kim SW, Ryang DW, Sung YK, Kim KY, J. Korean Soc. Medical Biological Eng., 8, 199 (1987)
Nagaoka S, Mori Y, Takiuchi H, Yokota K, Tanzawa H, Nishu S, "Polymers as Biomaterials," S.W. Shalaby, A.S. Hoffman, B.D. Ratner and T.A. Horbett, Ed., pp. 361-374, Plenum Press (1984)
Nagaoka S, Kurumatani H, Mori Y, Tanzawa H, J. Bioactive Compatible Polym., 4, 323 (1989)
Park KD, Okano T, Nojiri C, Kim SW, J. Biomed. Mater. Res., 22, 977 (1988)
Takahara A, Jo NJ, Kajiyama T, J. Biomater. Sci.-Polym. Ed., 1, 17 (1989)
Lee JH, Andrade JD, "Surface Properties of Aqueous PEO/PPO Block Copolymer Surfactants," in Polymer Surface Dynamics, J.D. Andrade (Ed.), Plenum Press, New York, pp. 119-136 (1988)
Fuller WD, Verlander MS, Goodman M, Biopolymers, 15, 869 (1976)
Alter JE, Taylor GT, Scheraga HA, Macromolecules, 5, 739 (1972)
Doty P, Bradbury JH, Holtzer AM, J. Am. Chem. Soc., 78, 947 (1956)
Holtzwarth G, Doty P, J. Am. Chem. Soc., 87, 218 (1965)

[1] Sakurai Y, Akaike T, Kataoka K, Okano T, "Interfacial Phenomena in Biomaterial Chemistry," A. Nakajima and E. Goldberg, Eds., Academic, New York, pp. 335-379 (1980)

[2] Andrade JD, Med. Instrum., 7, 110 (1973)

[3] Okano T, Nishiyama S, Shinohara I, Akaike T, Sakurai Y, Kataoka K, Tsuruta T, Kuwana K, Miyata S, Artificial Org., 3, 253 (1979)

[4] Kim SW, Ebert CD, Lin JY, Mcrea JC, ASAIO J., 6, 76 (1983)

[5] Heyman PW, Cho CS, McRea JC, Olsen DW, Kim SW, J. Biomed. Mater. Res., 19, 419 (1985)

[6] Lyman DJ, Hill DW, Stirk RK, Adamson C, Mooney BR, Trans. Am. Soc. Artif. Intern. Org., 18, 19 (1972)

[7] Okano T, Nishiyama S, Shinohara I, Akaike T, Sakurai Y, Kataoka K, Tsuruta T, J. Biomed. Mater. Res., 15, 393 (1981)

[8] Sawyer PN, Burrowes C, Ogoniak J, Smith AO, Wesolowski SA, Trans. Am. Soc. Artif. Intern. Organs., 10, 316 (1964)

[9] Nakajima A, Hayashi T, Kugo K, Shinoda K, Macromolecules, 12, 840 (1979)

[10] Nakajima A, Kugo K, Hayashi T, Macromolecules, 12, 844 (1979)

[11] Nakajima A, Kugo K, Hayashi T, Polym. J., 11, 995 (1979)

[12] Chen GW, Hayashi T, Nakajima A, Polym. J., 13, 433 (1981)

[13] Kugo K, Hayashi T, Nakajima A, Polym. J., 14, 401 (1982)

[14] Kugo K, Murashima M, Hayashi T, Nakajima A, Polym. J., 15, 267 (1983)

[15] Okano T, Uruno M, Sugiyama N, Shimada M, Shinohara I, Kataoka K, Sakurai Y, J. Biomed. Mater. Res., 20, 1035 (1986)

[16] Nishimura T, Sato Y, Yokoyama M, Okuya M, Inoue S, Kataoka K, Okano T, Sakurai Y, Makromol. Chem., 185, 2079 (1984)

[17] Cho CS, Kim SW, Sung YK, Kim KY, Makromol. Chem., 189, 1505 (1988)

[18] Cho CS, Song SC, Kim SW, Ryang DW, Sung YK, Kim KY, J. Korean Soc. Medical Biological Eng., 8, 199 (1987)

[19] Nagaoka S, Mori Y, Takiuchi H, Yokota K, Tanzawa H, Nishu S, "Polymers as Biomaterials," S.W. Shalaby, A.S. Hoffman, B.D. Ratner and T.A. Horbett, Ed., pp. 361-374, Plenum Press (1984)

[20] Nagaoka S, Kurumatani H, Mori Y, Tanzawa H, J. Bioactive Compatible Polym., 4, 323 (1989)

[21] Park KD, Okano T, Nojiri C, Kim SW, J. Biomed. Mater. Res., 22, 977 (1988)

[22] Takahara A, Jo NJ, Kajiyama T, J. Biomater. Sci.-Polym. Ed., 1, 17 (1989)

[23] Lee JH, Andrade JD, "Surface Properties of Aqueous PEO/PPO Block Copolymer Surfactants," in Polymer Surface Dynamics, J.D. Andrade (Ed.), Plenum Press, New York, pp. 119-136 (1988)

[24] Fuller WD, Verlander MS, Goodman M, Biopolymers, 15, 869 (1976)

[25] Alter JE, Taylor GT, Scheraga HA, Macromolecules, 5, 739 (1972)

[26] Doty P, Bradbury JH, Holtzer AM, J. Am. Chem. Soc., 78, 947 (1956)

[27] Holtzwarth G, Doty P, J. Am. Chem. Soc., 87, 218 (1965)