Assembly of amphiphilic poly[2‐(methacryloyloxy)ethyl phosphorylcholine] with cholesteryl moieties as terminal groups

Assembly of amphiphilic poly[2‐(methacryloyloxy)ethyl phosphorylcholine] with cholesteryl moieties as terminal groups
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以胆固醇基为端基的两亲性聚[2-(甲基丙烯酰氧基)乙基磷酰胆碱]的组装

DOI:
10.1002/pola.10746
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发表时间:
2003
期刊:
Journal of Polymer Science Part A
影响因子:
--
通讯作者:
Takako Matsumoto
Takako Matsumoto
中科院分区:
--
文献类型:
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作者:
K. Sugiyama;K. Shiraishi;Takako Matsumoto

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聚[2-在聚合物末端具有一个胆固醇侧基部分的(甲基丙烯酰氧基)乙基磷酰胆碱(PMPC)(PMPC-Chol-I和PMPC-Chol-II)和两个聚合物末端的两个侧链胆固醇基部分作为端基(PMPC-2Chol-I和PMPC-2Chol-II)是通过2-甲基-N-(2-甲基-N-苯基)氨基)苯基)-2-甲基-N-(2-甲基-N-苯基)氨基)苯甲酸酯的自由基聚合制备的。分别以巯基乙醇或硫代胆固醇为链转移剂,以4,4 ′-偶氮二[(3-胆固醇)-4-氰基戊酸酯]为引发剂,合成了(甲基丙烯酰氧基)乙基磷酰胆碱。用荧光光谱和核磁共振氢谱分析了PMPC-2Chol和PMPC-Chol的自组织结构。聚合度(Pn)为91的PMPC-Chol-I和Pn值为165的PMPC-2Chol-I的临界胶束浓度分别为250和27 mg L−1。在存在PMPC-2Chol的情况下,根据凝血酶和合成底物S-2238的酶促反应的米氏常数(Km)评价PMPC-2Chol的血液相容性。在不存在链转移剂的情况下,用2,2 ′-偶氮二异丁腈引发的PMPC-2Chol-I(Pn = 165)、PMPC-2Chol-II(Pn = 38)和PMPC(特性粘度为0.54 dL g−1)的Km分别为0.07、0.05和0.56。作为药物模型的PMPC-2Chol-II和胆固醇的混合物形成层片状复合物,其晶面间距d = 35.2 A。© 2003 Wiley Periodicals,Inc. J Polym Sci A部分:Polym Chem 41:1992-2000,2003
Poly[2-(methacryloyloxy)ethyl phosphorylcholine]s (PMPCs) with one pendant cholesteryl moiety at the polymer end (PMPC-Chol-I and PMPC-Chol-II) and two pendant cholesteryl moieties at both polymer ends as terminal groups (PMPC-2Chol-I and PMPC-2Chol-II) were prepared by the radical polymerization of 2-(methacryloyloxy)ethyl phosphorylcholine initiated with 4,4′-azobis[(3-cholesteryl)-4-cyanopentanoate] in the presence of 2-mercaptoethanol or thiocholesterol as chain-transfer reagents, respectively. The self-organization of PMPC-Chol and PMPC-2Chol was analyzed with fluorescence and 1H NMR measurements. The critical micelle concentrations of PMPC-Chol-I with a degree of polymerization (Pn) of 91 and of PMPC-2Chol-I with a Pn value of 165 were 250 and 27 mg L−1, respectively. The blood compatibility of PMPC-2Chol was evaluated from the Michaelis constant (Km) for the enzymatic reaction of thrombin and a synthetic substrate, S-2238, in the presence of PMPC-2Chol. Km was 0.07, 0.05, and 0.56 for PMPC-2Chol-I with Pn = 165, PMPC-2Chol-II with Pn = 38, and PMPC (an intrinsic viscosity of 0.54 dL g−1) initiated with 2,2′-azobisisobutyronnitrile in the absence of chain transfer agent, respectively. A mixture of PMPC-2Chol-II and cholesterol as a drug model formed a lamellar type of complex with an interplanar spacing of d = 35.2 A. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1992–2000, 2003