化学学报 ›› 2016, Vol. 74 ›› Issue (9): 752-757.DOI: 10.6023/A16060281 上一篇    下一篇

研究论文

含冠醚双亲共聚物纳米聚集体的制备及性能

张瑀健a,b, 谢彬b, 姜涛a   

  1. a 天津科技大学 材料科学与化学工程学院 天津 300457;
    b 中国石油石油化工研究院 合成树脂加工应用研究室 北京 100195
  • 收稿日期:2016-06-07 出版日期:2016-09-10 发布日期:2016-09-06
  • 通讯作者: 姜涛 E-mail:jiangtao@tust.edu.cn
  • 基金资助:

    项目受天津市应用基础与前沿技术研究计划重点项目(16JCZDJC31600)资助.

Preparation and Properties of Crown Ethers Containing Amphiphilic Copolymer Nano-aggregates

Zhang Yu-Jiana,b, Xie Binb, Jiang Taoa   

  1. a Tianjin University of Science and Technology, Materials Science and Chemical Engineering Institute, Tianjin 300457, China;
    b Petrochemical Research Institute of PetroChina, Synthetic Resins and Processing Applications Lab, Beijing 100195, China
  • Received:2016-06-07 Online:2016-09-10 Published:2016-09-06
  • Supported by:

    Key Projects of Application Foundation and Frontier Technology Research Program of Tianjin Municipality (16JCZDJC31600).

模拟DNA化学结构,设计并合成了双亲共聚物聚(2,2'-(1,10-二氮杂-[18]冠-6-1,10-二基)二乙基5-((腺嘌呤-9-基)甲基)间苯二甲酸酯)(PDCAI),利用扫描电镜(SEM)观测了其在水溶液中的自组织形态,采用红外光谱法(FT-IR)研究了其与底物胸腺嘧啶(thymine)的氢键识别,并以变温红外进一步证实和考察了氢键的形成及断裂. 同时,尝试了利用K+对PDCAI的自组织形态和氢键识别进行了调控,结果表明:在水溶液中PDCAI自发聚集成条带状聚集体,利用K+调控可使其聚集形态转变为棒状、纳米管状或螺旋棒状;在水溶液中底物thymine的C2=O与PDCAI进行了氢键识别,而通过K+调控,氢键识别基变为thymine的C4=O,说明PDCAI聚集形态的转变导致thymine在与其识别过程中进行识别构象的重组织. PDCAI的研制对研究揭示聚合物自发形成螺旋的分子特征、制备螺旋型聚合物、研制新型药物载体及功能调控具有参考意义.

关键词: 药物载体, 聚集体, 氢键, 离子调控

In this paper, an amphiphilic copolymer poly(2,2'-(1,10-diaza-[18]crown-6-1,10-diyl)diethyl 5-((adenin-9-yl)- methyl)isophthalate) (PDCAI) was designed and synthesized by simulating the chemical structure of DNA. We observed its self-organized morphology in the aqueous solution and in potassium solution with scanning electron microscopy (SEM), amphiphilic copolymer PDCAI spontaneously aggregated into strip aggregates in aqueous solution, and which could change into a rod, nanotube or helical rod aggregates in KNO3 solution. In addition, the molecular recognition between copolymer PDCAI and thymine substrate has been studied via FT-IR, and it is found that C2=O of thymine had recognized with PDCAI through complementary nucleobases in aqueous solution, the C2=O stretching band of thymine at 1737 cm-1 shifted to 1710 cm-1 after recognition, however, the band of the C4=O of thymine did not change at 1677 cm-1. Meanwhile we attempted to regulate the molecular recognition of copolymer PDCAI with thymine substrate with K+, we surprisingly found that hydrogen bonding occurs on C4=O of thymine when it recognized with PDCAI in KNO3 solution, the C4=O stretching band of thymine at 1677 cm-1 shifted to 1671 cm-1, however, the band of the C2=O of thymine did not change at 1737 cm-1 after recognition. It proves that the recognizing conformation of thymine re-organized during identification process due to the transition of aggregation form of PDCAI. And we further confirmed and studied the hydrogen bond formation and fracture process by variable temperature FT-IR, which formed at room temperature gradually broke while temperature rising from 25℃ up to 115℃, when temperature was above 115℃, hydrogen bonds broke completely, thymine and PDCAI return to their pre-recognition state. The formations of hydrogen bonds between adenine in the polymer and thymine substrate in nanospheres could enhance their interaction and loading capacity. The results have reference value for research of molecular characteristics of polymer which spontaneously formed spiral, preparation of helical polymer, and nucleic acid imitation drug carriers and its function regulation.

Key words: drug carriers, aggregates, hydrogen bond, ion regulation