化学学报 ›› 2013, Vol. 71 ›› Issue (04): 549-554.DOI: 10.6023/A13010087 上一篇    下一篇

研究论文

DNA-树状聚脂肪醚杂化体的合成及组装性能研究

赵智勇a,c, 吴芬a, 杨忠强b, 刘冬生b, 范青华a   

  1. a 中国科学院化学研究所分子识别与功能重点实验室 北京分子科学国家实验室 北京 100190;
    b 清华大学化学系 有机光电子与分子工程教育部重点实验室 北京 100084;
    c 中国科学院大学 北京 100049
  • 收稿日期:2013-01-17 出版日期:2013-04-14 发布日期:2013-03-01
  • 通讯作者: 杨忠强, 范青华 E-mail:fanqh@iccas.ac.cn; zyang@tsinghua.edu.cn
  • 基金资助:

    项目受国家自然科学基金(Nos. 21232008, 21174077, 91027046)和973项目(No. 2013CB932800)资助.

Synthesis and Self-Assembly of DNA-Aliphatic Polyether Dendron Hybrids

Zhao Zhiyonga,c, Wu Fena, Yang Zhongqiangb, Liu Dongshengb, Fan Qing-Huaa   

  1. a Beijing National Laboratory for Molecular Sciences (BNLMS), CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences (CAS), Beijing 100190, China;
    b Key Laboratory of Organic Optoelectronics & Molecular Engineering of the Ministry of Education,Department of Chemistry, Tsinghua University, Beijing 100084, China;
    c University of Chinese Academy of Sciences, Beijing 100049, China
  • Received:2013-01-17 Online:2013-04-14 Published:2013-03-01
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 21232008, 21174077, 91027046) and 973 Program (No. 2013CB932800).

通过半固相合成方法得到一类新型的具柔性骨架的树状聚脂肪醚(PMDC)与DNA的嵌段共聚物, 也称为DNA-树状聚脂肪醚杂化体, 其结构通过了MALDI-TOF MS、HPLC和聚丙烯酰胺凝胶电泳(PAGE)表征. 研究证明, 通过调节DNA-树状聚脂肪醚杂化体的结构和组装的溶剂体系, 可以得到各种不同的有序聚集体(球形胶束、纳米纤维等), 这些组装形貌均通过透射电镜(TEM)、原子力显微镜(AFM)和动态光散射(DLS)进行表征; 荧光包裹实验和DNA互补配对实验不仅证明了疏水树状聚脂肪醚位于组装体内核、DNA处于外壳的组装机理, 也说明这类DNA-树状聚脂肪醚杂化体将在疏水药物运输和纳米技术等领域具有潜在的应用.

关键词: DNA-树状分子, 两亲分子, 自组装, 球形胶束, 纤维

A new kind of amphiphilic DNA-aliphatic polyether dendron hybrids consisting of a flexible hydrophobic polyether dendron and a single stranded DNA are synthesized, which are characterized by MALDI-TOF mass spectroscopy, HPLC and polyacrylamide gel electrophoresis (PAGE). In aqueous solution, as DNA length shortens from 24 mer to 18 mer, to 12 mer, to 6 mer, the hydrophilic DNA content in the DNA-aliphatic polyether dendron hybrid decreases, the morphology of the aggregates change from spherical micelles to nanofibers, and to irregular clusters. These different assemblies from DNA-aliphatic polyether dendron hybrids in aqueous solution are depended on the hydrophobic/hydrophilic ratio between the polyether dendron skeleton and DNA strand. However, when adding 1/10 (V/V) organic solvents such as dichloromethane (DCM), diethyl ether (EtOEt) or tetrahydrofuran (THF) into aqueous solution and after the assembling process that the sample solution is heated to 90 ℃ for 30 min and subsequently cooled to room temperature overnight, the third generation dendron conjugated 18 mer DNA hybrid could assemble into nanofibers. Meanwhile, in the THF/H2O (1∶10, V/V) mixed solvents, with the same assembling process, as different dendron generations (the second or third generation) and different DNA lengths (6 mer, 12 mer, 18 mer or 24 mer) in the hybrids, all these hybrids could assemble into long nanofibers. The assembled structures have been characterized by transmission electron microscopy (TEM), atomic force microscope (AFM), dynamic light scattering (DLS) and fluorescent experiments. Subsequently, we verified the assembling mechanism that the spherical micelles and nanofibers contain a hydrophobic dendron core and a hydrophilic DNA shell by hydrophobic fluorescent molecule Nile Red encapsulation experiment and precise DNA hybridization to load gold nanoparticles at a size of 10 nm. The hybridization property of DNA at the shell associated with the encapsulation ability of dendron at the inner core indicated the potential application in gene or drug delivery and nanotechnology.

Key words: DNA-dendron, amphiphile, self-assembly, spherical micelle, nanofiber