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脱氢枞酸三羟甲基丙烷-丙二酸聚酯的制备及其胶束聚集研究

Preparation of Poly(Trimethylolpropane Dehydroabietate Malonate) and Its Micellar Aggregation

  • 摘要: 以脱氢枞酸三羟甲基丙烷酯(DATE)和丙二酸(MA)为原料,成功制备了一种新型的具有生物相容性的脱氢枞酸三羟甲基丙烷-丙二酸聚酯(DMPE),利用多种方法表征了DMPE的物理化学特性,分析了DMPE的细胞毒性,探讨了DMPE链在降温和升温过程中的聚集和解聚特性,以及恒温条件下DMPE胶束聚集的动力学参数。研究结果表明:DMPE已被成功合成,其数均相对分子质量为3 900,重均相对分子质量为6 300,多分散系数为1.62,聚合度为7.8;DMPE在400 nm处有散射峰,320 ℃左右开始分解,450 ℃基本完全分解。DMPE水溶液在低浓度时对L929细胞具有增殖作用,随着浓度增加,细胞存活率逐渐降低。DMPE链在降温过程中聚集形成胶束,聚集温度随浓度增加而增大;而在升温过程,聚集胶束逐渐解聚,并表现出明显的滞后现象。动力学研究发现低温有利于胶束的聚集,当温度为3 ℃时,Avrami指数(n)为5.79,速率常数(kp)为1.78×10-11,指前因子(A)为1.55×1022,表观活化能(E)为-127.12 kJ/mol。DMPE具有温度响应性及生物相容性使其可作为表面活性剂与药物载体。

     

    Abstract: A novel biocompatible dehydrogenated trimethylolpropane polyester(DMPE) was successfully prepared from trimethylolpropane dehydroabietate(DATE) and malonic acid(MA). The physicochemical properties of DMPE were characterized by a variety of methods and its cytotoxicity was investigated. The aggregation and de-aggregation characteristics of DMPE chains during cooling and heating process, and the kinetic parameters of DMPE micellar aggregation under constant temperature conditions were also studied. The results showed that DMPE has been successfully synthesized, and the number average molecular weight, the weight average molecular weight, and the degree of polymerization were 3 900, 6 300, and 7.8. Rayleigh scattering spectroscopy showed that DMPE had a scattering peak at 400 nm, and TG and analysis showed that DMPE started to compose at about 320 ℃, and completely degraded at 450 ℃. Moreover, DMPE aqueous solution had a proliferative effect on L929 cells at a low concentration, and the cell viability gradually decreased with the increasing concentration. During the cooling process, the DMPE chains aggregated to form micellars, and the aggregation temperature increased with the increasing concentration. However in the heating process, the aggregated micellars gradually de-aggregated and presented an obvious hysteresis. Kinetic studies indicated that the low temperature was conducive to the aggregation of micells. When the temperature was 3 ℃, the Avrami index(n) was 5.79, rate constant(kp) was 1.78×10-11, the pre-exponential factor(A) was 1.55×1022, and the apparent activation energy(Ea) was -127.12 kJ/mol. The temperature responsiveness and biocompatibility of DMPE make it as a surfactant and drug carrier.

     

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